CHAPTER 2
The First Law
The release of energy can be used to provide heat when a fuel
burns in a furnace, to produce mechanical work when a fuel
burns in an engine, and to generate electrical work when a
chemical reaction pumps electrons through a circuit. In chem-
istry, we encounter reactions that can be harnessed to provide
heat and work, reactions that liberate energy that is unused but
which give products we require, and reactions that constitute
the processes of life. Thermodynamics, the study of the trans-
formations of energy, enables us to discuss all these matters
quantitatively and to make useful predictions.
2A Internal energy
First, we examine the ways in which a system can exchange
energy with its surroundings in terms of the work it may do or
have done on it or the heat that it may produce or absorb. These
considerations lead to the definition of the ‘internal energy’, the
total energy of a system, and the formulation of the ‘First Law’
of thermodynamics, which states that the internal energy of an
isolated system is constant.
2B Enthalpy
The second major concept of the chapter is ‘enthalpy’, which is a
very useful book-keeping property for keeping track of the heat
output (or requirements) of physical processes and chemical
reactions that take place at constant pressure. Experimentally,
changes in internal energy or enthalpy may be measured by
techniques known collectively as ‘calorimetry’.
2C Thermochemistry
‘Thermochemistry’ is the study of heat transactions dur-
ing chemical reactions. We describe both computational and
experimental methods for the determination of enthalpy
changes associated with both physical and chemical changes.
2D State functions and exact differentials
We also begin to unfold some of the power of thermodynamics
by showing how to establish relations between different prop-
erties of a system. We see that one very useful aspect of ther-
modynamics is that a property can be measured indirectly by
measuring others and then combining their values. The rela-
tions we derive also enable us to discuss the liquefaction of
gases and to establish the relation between the heat capacities of
a substance under different conditions.
2E Adiabatic changes
‘Adiabatic’ processes occur without transfer of energy as heat.
We focus on adiabatic changes involving perfect gases because
they figure prominently in our presentation of thermodynamics.
What is the impact of this material?
Concepts of thermochemistry apply to the chemical reactions
associated with the conversion of food into energy in organisms,
and so form a basis for the discussion of bioenergetics. In Impact
I2.1, we explore some of the thermochemical calculations
related to the metabolism of fats, carbohydrates, and proteins.
To read more about the impact of this
material, scan the QR code, or go to
bcs.whfreeman.com/webpub/chemistry/
pchem10e/impact/pchem-2-1.html
2A Internal energy

Contents ➤➤ What is the key idea?

2A.1 Work, heat, and energy 65 The total energy of an isolated system is constant.
(a) Operational definitions 65
Brief illustration 2A.1: Combustions in adiabatic ➤➤ What do you need to know already?
and diathermic containers 65 This Topic makes use of the discussion of the properties of
(b) The molecular interpretation of heat and work 66 gases (Topic 1A), particularly the perfect gas law. It builds
2A.2 The definition of internal energy 66 on the definition of work given in Foundations B.
(a) Molecular interpretation of internal energy 67
Brief illustration 2A.2: The internal energy of a
perfect gas 67
(b) The formulation of the First Law 67 For the purposes of thermodynamics, the universe is divided
Brief illustration 2A.3: Changes in internal energy 68 into two parts, the system and its surroundings. The system
2A.3 Expansion work 68 is the part of the world in which we have a special interest. It
(a) The general expression for work 68 may be a reaction vessel, an engine, an electrochemical cell,
Brief illustration 2A.4: The work of extension 69 a biological cell, and so on. The surroundings comprise the
(b) Expansion against constant pressure 69 region outside the system and are where we make our measure-
Example 2A.1: Calculating the work of gas ments. The type of system depends on the characteristics of the
production 69 boundary that divides it from the surroundings (Fig. 2A.1). If
(c) Reversible expansion 70 matter can be transferred through the boundary between the
(d) Isothermal reversible expansion 70 system and its surroundings the system is classified as open. If
Brief illustration 2A.5: The work of isothermal matter cannot pass through the boundary the system is clas-
reversible expansion 70 sified as closed. Both open and closed systems can exchange
2A.4 Heat transactions 71 energy with their surroundings. For example, a closed system
(a) Calorimetry 71 can expand and thereby raise a weight in the surroundings; a
Brief illustration 2A.6: Electrical heating 72 closed system may also transfer energy to the surroundings if
(b) Heat capacity 72 they are at a lower temperature. An isolated system is a closed
Brief illustration 2A.7: Heat capacity 73 system that has neither mechanical nor thermal contact with its
Brief illustration 2A.8: The determination of a heat surroundings.
capacity 73
Checklist of concepts 74
Checklist of equations 74
Energy

Energy
Matter

➤➤ Why do you need to know this material? Open Closed Isolated

The First Law of thermodynamics is the foundation of the

discussion of the role of energy in chemistry. Wherever
we are interested in the generation or use of energy in
physical transformations or chemical reactions, lying
in the background are the concepts introduced by the
First Law.
(a) (b) (c)
Figure 2A.1 (a) An open system can exchange matter and
energy with its surroundings. (b) A closed system can exchange
energy with its surroundings, but it cannot exchange matter.
(c) An isolated system can exchange neither energy nor matter
with its surroundings.

2A.1 Work, heat, and energy
Although thermodynamics deals with observations on bulk
systems, it is immeasurably enriched by understanding the
molecular origins of these observations. In each case we shall
set out the bulk observations on which thermodynamics is
based and then describe their molecular interpretations.
(a) Operational definitions
The fundamental physical property in thermodynamics is
work: work is done to achieve motion against an oppos-
ing force. A simple example is the process of raising a weight
against the pull of gravity. A process does work if in principle it
can be harnessed to raise a weight somewhere in the surround-
ings. An example of doing work is the expansion of a gas that
pushes out a piston: the motion of the piston can in principle
be used to raise a weight. A chemical reaction that drives an
electric current through a resistance also does work, because
the same current could be passed through a motor and used to
raise a weight.
The energy of a system is its capacity to do work. When work
is done on an otherwise isolated system (for instance, by com-
pressing a gas or winding a spring), the capacity of the system to
do work is increased; in other words, the energy of the system
is increased. When the system does work (i.e. when the piston
moves out or the spring unwinds), the energy of the system is
reduced and it can do less work than before.
Experiments have shown that the energy of a system may be
changed by means other than work itself. When the energy of a
system changes as a result of a temperature difference between
the system and its surroundings we say that energy has been
transferred as heat. When a heater is immersed in a beaker
of water (the system), the capacity of the system to do work
increases because hot water can be used to do more work than
the same amount of cold water. Not all boundaries permit the
transfer of energy even though there is a temperature differ-
ence between the system and its surroundings. Boundaries that
do permit the transfer of energy as heat are called diathermic;
those that do not are called adiabatic.
An exothermic process is a process that releases energy
as heat into its surroundings. All combustion reactions are
exothermic. An endothermic process is a process in which
energy is acquired from its surroundings as heat. An example
of an endothermic process is the vaporization of water. To
avoid a lot of awkward language, we say that in an exother-
mic process energy is transferred ‘as heat’ to the surround-
ings and in an endothermic process energy is transferred
‘as heat’ from the surroundings into the system. However, it
must never be forgotten that heat is a process (the transfer of
energy as a result of a temperature difference), not an entity.
An endothermic process in a diathermic container results in
2A Internal energy 65
energy flowing into the system as heat to restore the tempera-
ture to that of the surroundings. An exothermic process in a
similar diathermic container results in a release of energy as
heat into the surroundings. When an endothermic process
takes place in an adiabatic container, it results in a lowering
of temperature of the system; an exothermic process results
in a rise of temperature. These features are summarized in
Fig. 2A.2.
Heat
Heat
Endothermic Exothermic Endothermic Exothermic
process process
process process
(a) (b) (c) (d)
Figure 2A.2 (a) When an endothermic process occurs in
an adiabatic system, the temperature falls; (b) if the process
is exothermic, then the temperature rises. (c) When an
endothermic process occurs in a diathermic container, energy
enters as heat from the surroundings, and the system remains
at the same temperature. (d) If the process is exothermic, then
energy leaves as heat, and the process is isothermal.
Brief illustration 2A.1 Combustions in adiabatic and
diathermic containers
Combustions are chemical reactions in which substances
react with oxygen, normally with a flame. An example is the
combustion of methane gas, CH4(g):
CH 4 (g) + 2 O2 (g ) → CO2 (g ) + 2 H2O(l)
All combustions are exothermic. Although the temperature
typically rises in the course of the combustion, if we wait long
enough, the system returns to the temperature of its surround-
ings so we can speak of a combustion ‘at 25 °C’, for instance.
If the combustion takes place in an adiabatic container, the
energy released as heat remains inside the container and
results in a permanent rise in temperature.
Self-test 2A.1 How may the isothermal expansion of a gas be
achieved?
Answer: Immerse the system in a water bath
66 2 The First Law
The molecular interpretation of heat
(b)
and work
In molecular terms, heating is the transfer of energy that makes
use of disorderly, apparently random, molecular motion in the
surroundings. The disorderly motion of molecules is called
thermal motion. The thermal motion of the molecules in the
hot surroundings stimulates the molecules in the cooler sys-
tem to move more vigorously and, as a result, the energy of
the system is increased. When a system heats its surroundings,
molecules of the system stimulate the thermal motion of the
molecules in the surroundings (Fig. 2A.3).
In contrast, work is the transfer of energy that makes use
of organized motion in the surroundings (Fig. 2A.4). When a
weight is raised or lowered, its atoms move in an organized way
(up or down). The atoms in a spring move in an orderly way
Surroundings
Energy
Energy
Energy
System
Figure 2A.3 When energy is transferred to the surroundings
as heat, the transfer stimulates random motion of the atoms
in the surroundings. Transfer of energy from the surroundings
to the system makes use of random motion (thermal motion)
in the surroundings.
Surroundings
Energy
Energy
Energy
System
Figure 2A.4 When a system does work, it stimulates orderly
motion in the surroundings. For instance, the atoms shown
here may be part of a weight that is being raised. The ordered
motion of the atoms in a falling weight does work on the
system.
when it is wound; the electrons in an electric current move in
the same direction. When a system does work it causes atoms
or electrons in its surroundings to move in an organized way.
Likewise, when work is done on a system, molecules in the sur-
roundings are used to transfer energy to it in an organized way,
as the atoms in a weight are lowered or a current of electrons is
passed.
The distinction between work and heat is made in the sur-
roundings. The fact that a falling weight may stimulate thermal
motion in the system is irrelevant to the distinction between
heat and work: work is identified as energy transfer making use
of the organized motion of atoms in the surroundings, and heat
is identified as energy transfer making use of thermal motion
in the surroundings. In the adiabatic compression of a gas, for
instance, work is done on the system as the atoms of the com-
pressing weight descend in an orderly way, but the effect of the
incoming piston is to accelerate the gas molecules to higher
average speeds. Because collisions between molecules quickly
randomize their directions, the orderly motion of the atoms of
the weight is in effect stimulating thermal motion in the gas.
We observe the falling weight, the orderly descent of its atoms,
and report that work is being done even though it is stimulating
thermal motion.
2A.2 The definition of internal energy
In thermodynamics, the total energy of a system is called its
internal energy, U. The internal energy is the total kinetic and
potential energy of the constituents (the atoms, ions, or mole-
cules) of the system. It does not include the kinetic energy aris-
ing from the motion of the system as a whole, such as its kinetic
energy as it accompanies the Earth on its orbit round the Sun.
That is, the internal energy is the energy ‘internal’ to the sys-
tem. We denote by ΔU the change in internal energy when a
system changes from an initial state i with internal energy Ui to
a final state f of internal energy Uf :
∆U = U f −U i (2A.1)
Throughout thermodynamics, we use the convention that
ΔX = Xf – Xi, where X is a property (a ‘state function’) of the
system.
The internal energy is a state function in the sense that its
value depends only on the current state of the system and is
independent of how that state has been prepared. In other
words, internal energy is a function of the properties that deter-
mine the current state of the system. Changing any one of the
state variables, such as the pressure, results in a change in inter-
nal energy. That the internal energy is a state function has con-
sequences of the greatest importance, as we shall start to unfold
in Topic 2D.

The internal energy is an extensive property of a system (a
property that depends on the amount of substance present,
Foundations A) and is measures in joules (1 J = 1 kg m2 s−2).
The molar internal energy, Um, is the internal energy divided
by the amount of substance in a system, Um = U/n; it is an
intensive property (a property independent of the amount
of substance) and commonly reported in kilojoules per mole
(kJ mol−1).
(a) Molecular interpretation of internal
energy
A molecule has a certain number of motional degrees of free-
dom, such as the ability to translate (the motion of its centre
of mass through space), rotate around its centre of mass, or
vibrate (as its bond lengths and angles change, leaving its cen-
tre of mass unmoved). Many physical and chemical properties
depend on the energy associated with each of these modes of
motion. For example, a chemical bond might break if a lot of
energy becomes concentrated in it, for instance as vigorous
vibration.
The ‘equipartition theorem’ of classical mechanics intro-
duced in Foundations B can be used to predict the contribu-
tions of each mode of motion of a molecule to the total energy
of a collection of non-interacting molecules (that is, of a perfect
gas, and providing quantum effects can be ignored). For trans-
lation and rotational modes the contribution of a mode is pro-
portional to the temperature, so the internal energy of a sample
increases as the temperature is raised.
Brief illustration 2A.2 The internal energy of a perfect gas
In Foundations B it is shown that the mean energy of a mol-
ecule due to its translational motion is 23 kT and therefore
to the molar energy of a collection the contribution is 23 RT .
Therefore, considering only the translational contribution to
internal energy,
U m (T ) = U m (0) + 23 N A kT = U m (0) + 23 RT
where Um(0), the internal energy at T = 0, can be greater than
zero (see, for example, Chapter 8). At 25 °C, RT = 2.48 kJ mol−1,
so the translational motion contributes 3.72 kJ mol−1 to the
molar internal energy of gases.
Self-test 2A.2 Calculate the molar internal energy of carbon
dioxide at 25 °C, taking into account its translational and rota-
tional degrees of freedom.
Answer: Um(T) = Um(0) + 25 RT
The contribution to the internal energy of a collection of
perfect gas molecules is independent of the volume occupied
by the molecules: there are no intermolecular interactions in a
2A Internal energy 67
perfect gas, so the distance between the molecules has no effect
on the energy. That is, the internal energy of a perfect gas is inde-
pendent of the volume it occupies.
The internal energy of interacting molecules in condensed
phases also has a contribution from the potential energy of their
interaction, but no simple expressions can be written down in
general. Nevertheless, it remains true that as the temperature of
a system is raised, the internal energy increases as the various
modes of motion become more highly excited.
(b) The formulation of the First Law
It has been found experimentally that the internal energy of a
system may be changed either by doing work on the system or
by heating it. Whereas we may know how the energy transfer
has occurred (because we can see if a weight has been raised or
lowered in the surroundings, indicating transfer of energy by
doing work, or if ice has melted in the surroundings, indicat-
ing transfer of energy as heat), the system is blind to the mode
employed. Heat and work are equivalent ways of changing a sys-
tem’s internal energy. A system is like a bank: it accepts deposits
in either currency, but stores its reserves as internal energy. It
is also found experimentally that if a system is isolated from its
surroundings, then no change in internal energy takes place.
This summary of observations is now known as the First Law
of thermodynamics and is expressed as follows:
The internal energy of an isolated system is constant.
First Law of thermodynamics
We cannot use a system to do work, leave it isolated, and then
come back expecting to find it restored to its original state with
the same capacity for doing work. The experimental evidence
for this observation is that no ‘perpetual motion machine’, a
machine that does work without consuming fuel or using some
other source of energy, has ever been built.
These remarks may be summarized as follows. If we write w
for the work done on a system, q for the energy transferred as
heat to a system, and ΔU for the resulting change in internal
energy, then it follows that
∆U = q + w Mathematical statement of the First Law (2A.2)
Equation 2A.2 summarizes the equivalence of heat and work
and the fact that the internal energy is constant in an isolated
system (for which q = 0 and w = 0). The equation states that
the change in internal energy of a closed system is equal to the
energy that passes through its boundary as heat or work. It
employs the ‘acquisitive convention’, in which w and q are posi-
tive if energy is transferred to the system as work or heat and
are negative if energy is lost from the system. In other words,
we view the flow of energy as work or heat from the system’s
perspective.
68 2 The First Law
Brief illustration 2A.3
Changes in internal energy
If an electric motor produced 15 kJ of energy each second as
mechanical work and lost 2 kJ as heat to the surroundings,
then the change in the internal energy of the motor each sec-
ond is ΔU = –2 kJ – 15 kJ = –17 kJ. Suppose that, when a spring
was wound, 100 J of work was done on it but 15 J escaped to
the surroundings as heat. The change in internal energy of the
spring is ΔU = 100 J – 15 J = +85 J.
A note on good practice Always include the sign of ΔU
(and of ΔX in general), even if it is positive.
Self-test 2A.3 A generator does work on an electric heater by
forcing an electric current through it. Suppose 1 kJ of work is
done on the heater and it heats its surroundings by 1 kJ. What
is the change in internal energy of the heater?
Answer: 0
2A.3 Expansion work
The way is opened to powerful methods of calculation by
switching attention to infinitesimal changes of state (such as
infinitesimal change in temperature) and infinitesimal changes
in the internal energy dU. Then, if the work done on a system
is dw and the energy supplied to it as heat is dq, in place of eqn
2A.2 we have
dU = dq + dw (2A.3)
To use this expression we must be able to relate dq and dw to
events taking place in the surroundings.
We begin by discussing expansion work, the work arising
from a change in volume. This type of work includes the work
done by a gas as it expands and drives back the atmosphere.
Many chemical reactions result in the generation of gases (for
instance, the thermal decomposition of calcium carbonate or
the combustion of octane), and the thermodynamic character-
istics of the reaction depend on the work that must be done to
make room for the gas it has produced. The term ‘expansion
work’ also includes work associated with negative changes of
volume, that is, compression.
(a) The general expression for work
The calculation of expansion work starts from the definition
used in physics, which states that the work required to move
an object a distance dz against an opposing force of magnitude
|F| is
dw = − F dz Definition Work done (2A.4)
The negative sign tells us that, when the system moves an object
against an opposing force of magnitude |F|, and there are no
other changes, then the internal energy of the system doing the
work will decrease. That is, if dz is positive (motion to positive
z), dw is negative, and the internal energy decreases (dU in eqn
2A.3 is negative provided that dq = 0).
Now consider the arrangement shown in Fig. 2A.5, in which
one wall of a system is a massless, frictionless, rigid, perfectly
fitting piston of area A. If the external pressure is pex, the
magnitude of the force acting on the outer face of the piston
is |F| = pexA. When the system expands through a distance dz
against an external pressure pex, it follows that the work done is
dw = –pexAdz. The quantity Adz is the change in volume, dV, in
the course of the expansion. Therefore, the work done when the
system expands by dV against a pressure pex is
dw = − pex dV Expansion work (2A.5a)
To obtain the total work done when the volume changes from
an initial value Vi to a final value Vf we integrate this expression
between the initial and final volumes:
Vf
w=− ∫Vi
pex dV (2A.5b)
The force acting on the piston, pexA, is equivalent to the force
arising from a weight that is raised as the system expands. If the
system is compressed instead, then the same weight is lowered
in the surroundings and eqn 2A.5b can still be used, but now
Vf  < Vi. It is important to note that it is still the external pressure
that determines the magnitude of the work. This somewhat
perplexing conclusion seems to be inconsistent with the fact
that the gas inside the container is opposing the compression.
However, when a gas is compressed, the ability of the surround-
ings to do work is diminished by an amount determined by the
weight that is lowered, and it is this energy that is transferred
into the system.
Other types of work (for example, electrical work), which we
shall call either non-expansion work or additional work, have
External
pressure, pex
dz dV = Adz
Area, A
Pressure, p
Figure 2A.5 When a piston of area A moves out through a
distance dz, it sweeps out a volume dV = Adz. The external
pressure pex is equivalent to a weight pressing on the piston,
and the magnitude of the force opposing expansion is |F| = pex A.
 2A Internal energy 69

Table 2A.1 Varieties of work* pex

Pressure, p
Type of work dw Comments Units†
Expansion –pexdV pex is the external pressure Pa m3 Area = pexΔV
dV is the change in volume
Surface expansion γ dσ γ is the surface tension N m−1 m2
dσ is the change in area
Extension fdl f is the tension Nm Vi Volume, V Vf
dl is the change in length
Electrical ϕdQ ϕ is the electric potential VC
dQ is the change in charge pex pex

Qdϕ dϕ is the potential difference VC

Q is the charge transferred
Figure 2A.6 The work done by a gas when it expands against
* In general, the work done on a system can be expressed in the form dw = –|F|dz,
where |F| is the magnitude of a ‘generalized force’ and dz is a ‘generalized a constant external pressure, pex, is equal to the shaded area in
displacement’. this example of an indicator diagram.
† For work in joules (J). Note that 1 N m = 1 J and 1 V C = 1 J.

Vf

analogous expressions, with each one the product of an inten-

w = − pex ∫ Vi
dV = − pex (Vf − Vi )

sive factor (the pressure, for instance) and an extensive factor

(the change in volume). Some are collected in Table 2A.1. For
the present we continue with the work associated with chang-
ing the volume, the expansion work, and see what we can
extract from eqn 2A.5b.
Brief illustration 2A.4 The work of extension
To establish an expression for the work of stretching an elasto-
mer, a polymer that can stretch and contract, to an extension l
given that the force opposing extension is proportional to the
displacement from the resting state of the elastomer we write
|F| = k f x, where k f is a constant and x is the displacement. It
then follows from eqn 2A.4 that for an infinitesimal displace-
ment from x to x + dx, dw = −k f xdx. For the overall work of dis-
placement from x = 0 to the final extension l,
l
1 of this kind occurs when a gas expands into a vacuum.
0 ∫
w = − kf x d x = − kf l 2
2
Self-test 2A.4 Suppose the restoring force weakens as the elas-
tomer is stretched, and k f(x) = a – bx1/2 . Evaluate the work of
extension to l.
1 2
Answer: w = − 2 al 2 + 5 bl5/2
(b) Expansion against constant pressure
Suppose that the external pressure is constant throughout the
expansion. For example, the piston may be pressed on by the
atmosphere, which exerts the same pressure throughout the
expansion. A chemical example of this condition is the expan-
sion of a gas formed in a chemical reaction in a container that
can expand. We can evaluate eqn 2A.5b by taking the constant
pex outside the integral:
Therefore, if we write the change in volume as ΔV = Vf − Vi,
w = − pex ∆V Constant external pressure Expansion work (2A.6)
This result is illustrated graphically in Fig. 2A.6, which makes
use of the fact that an integral can be interpreted as an area. The
magnitude of w, denoted |w|, is equal to the area beneath the
horizontal line at p = pex lying between the initial and final vol-
umes. A pV-graph used to illustrate expansion work is called
an indicator diagram; James Watt first used one to indicate
aspects of the operation of his steam engine.
Free expansion is expansion against zero opposing force. It
occurs when pex = 0. According to eqn 2A.6,
w =0 Work of free expansion (2A.7)
That is, no work is done when a system expands freely. Expansion
Example 2A.1 Calculating the work of gas production
Calculate the work done when 50 g of iron reacts with hydro-
chloric acid to produce FeCl 2(aq) and hydrogen in (a) a closed
vessel of fixed volume, (b) an open beaker at 25 °C.
Method We need to judge the magnitude of the volume
change and then to decide how the process occurs. If there is
no change in volume, there is no expansion work however the
process takes place. If the system expands against a constant
external pressure, the work can be calculated from eqn 2A.6.
A general feature of processes in which a condensed phase
changes into a gas is that the volume of the former may usually
be neglected relative to that of the gas it forms.
Answer In (a) the volume cannot change, so no expansion
work is done and w = 0. In (b) the gas drives back the atmos-
phere and therefore w = −p ex ΔV. We can neglect the initial
70 2 The First Law

with its surroundings and the expansion is thermodynamically

volume because the final volume (after the production of gas)
is so much larger and ΔV = Vf − Vi ≈ Vf = nRT/pex, where n is the
amount of H2 produced. Therefore,
nRT
w = − pex ∆V ≈ − pex × = −nRT
pex
Because the reaction is Fe(s) + 2 HCl(aq) → FeCl 2(aq) + H2(g),
we know that 1 mol H2 is generated when 1 mol Fe is consumed,
and n can be taken as the amount of Fe atoms that react.
Because the molar mass of Fe is 55.85 g mol−1, it follows that
irreversible.
To achieve reversible expansion we set pex equal to p at each
stage of the expansion. In practice, this equalization could be
achieved by gradually removing weights from the piston so
that the downward force due to the weights always matches the
changing upward force due to the pressure of the gas. When we
set pex = p, eqn 2A.5a becomes
dw = − pex dV = − pdV Reversible expansion work (2A.8a)

50 g Although the pressure inside the system appears in this expres-

w=− × (8.3145 JK −1 mol −1 ) × (298 K )
55.85 g mol −1
≈ −2.2 kJ
The system (the reaction mixture) does 2.2 kJ of work driving
back the atmosphere. Note that (for this perfect gas system)
the magnitude of the external pressure does not affect the final
result: the lower the pressure, the larger the volume occupied
by the gas, so the effects cancel.
Self-test 2A.5 Calculate the expansion work done when 50 g of
water is electrolysed under constant pressure at 25 °C.
Answer: −10 kJ
sion for the work, it does so only because pex has been set equal
to p to ensure reversibility. The total work of reversible expan-
sion from an initial volume Vi to a final volume Vf is therefore
Vf
w=− ∫
Vi
pdV (2A.8b)
The integral can be evaluated once we know how the pressure of
the confined gas depends on its volume. Equation 2A.8b is the
link with the material covered in the Topics of Chapter 1 for, if
we know the equation of state of the gas, then we can express p
in terms of V and evaluate the integral.

(c) Reversible expansion (d) Isothermal reversible expansion

A reversible change in thermodynamics is a change that can Consider the isothermal, reversible expansion of a perfect gas.
be reversed by an infinitesimal modification of a variable. The The expansion is made isothermal by keeping the system in ther-
key word ‘infinitesimal’ sharpens the everyday meaning of the mal contact with its surroundings (which may be a constant-
word ‘reversible’ as something that can change direction. One temperature bath). Because the equation of state is pV = nRT,
example of reversibility that we have encountered already is the we know that at each stage p = nRT/V, with V the volume at that
thermal equilibrium of two systems with the same temperature. stage of the expansion. The temperature T is constant in an iso-
The transfer of energy as heat between the two is reversible thermal expansion, so (together with n and R) it may be taken
because, if the temperature of either system is lowered infini- outside the integral. It follows that the work of reversible isother-
tesimally, then energy flows into the system with the lower mal expansion of a perfect gas from Vi to Vf at a temperature T is
temperature. If the temperature of either system at thermal
Integral A.2
equilibrium is raised infinitesimally, then energy flows out of Vf dV  Vf
the hotter system. There is obviously a very close relationship w = −nRT ∫Vi V
= − nRT ln
Vi
between reversibility and equilibrium: systems at equilibrium Perfect gas,
are poised to undergo reversible change. reversible, Work of
expansion (2A.9)
Suppose a gas is confined by a piston and that the external isothermal
pressure, pex, is set equal to the pressure, p, of the confined gas.
Such a system is in mechanical equilibrium with its surround- Brief illustration 2A.5 The work of isothermal reversible
ings because an infinitesimal change in the external pressure
expansion
in either direction causes changes in volume in opposite direc-
tions. If the external pressure is reduced infinitesimally, the gas When a sample of 1.00 mol Ar, regarded here as a perfect gas,
expands slightly. If the external pressure is increased infini- undergoes an isothermal reversible expansion at 20.0 °C from
tesimally, the gas contracts slightly. In either case the change is 10.0 dm3 to 30.0 dm3 the work done is
reversible in the thermodynamic sense. If, on the other hand, 30.0 dm3
the external pressure differs measurably from the internal w = −(1.00 mol) × (8.3145 JK −1 mol −1 ) × (293.2 K) ln
10.0 dm3
pressure, then changing pex infinitesimally will not decrease it
= −2.68 kJ
below the pressure of the gas, so will not change the direction
of the process. Such a system is not in mechanical equilibrium

Self-test 2A.6 Suppose that attractions are important between
gas molecules, and the equation of state is p = nRT/V – n2a/V2.
Derive an expression for the reversible, isothermal expansion
of this gas. Is more or less work done on the surroundings when
it expands (compared with a perfect gas)?
Answer: w = −nRT ln(Vf/Vi) − n2a(1/Vf − 1/Vi); less
When the final volume is greater than the initial volume,
as in an expansion, the logarithm in eqn 2A.9 is positive and
hence w < 0. In this case, the system has done work on the sur-
roundings and there is a corresponding negative contribution
to its internal energy. (Note the cautious language: we shall see
later that there is a compensating influx of energy as heat, so
overall the internal energy is constant for the isothermal expan-
sion of a perfect gas.) The equations also show that more work
is done for a given change of volume when the temperature is
increased: at a higher temperature the greater pressure of the
confined gas needs a higher opposing pressure to ensure revers-
ibility and the work done is correspondingly greater.
We can express the result of the calculation as an indicator
diagram, for the magnitude of the work done is equal to the
area under the isotherm p = nRT/V (Fig. 2A.7). Superimposed
on the diagram is the rectangular area obtained for irreversible
expansion against constant external pressure fixed at the same
final value as that reached in the reversible expansion. More
work is obtained when the expansion is reversible (the area is
greater) because matching the external pressure to the internal
pressure at each stage of the process ensures that none of the
system’s pushing power is wasted. We cannot obtain more work
than for the reversible process because increasing the external
pressure even infinitesimally at any stage results in compres-
sion. We may infer from this discussion that, because some
pushing power is wasted when p > pex, the maximum work
pi
p = nRT/V
Pressure, p
pf
Vi Volume, V Vf
pi pf
Figure 2A.7 The work done by a perfect gas when it expands
reversibly and isothermally is equal to the area under the
isotherm p = nRT/V. The work done during the irreversible
expansion against the same final pressure is equal to the
rectangular area shown slightly darker. Note that the reversible
work is greater than the irreversible work.
2A Internal energy 71
available from a system operating between specified initial and
final states and passing along a specified path is obtained when
the change takes place reversibly.
We have introduced the connection between reversibility
and maximum work for the special case of a perfect gas under-
going expansion. In Topic 3A we see that it applies to all sub-
stances and to all kinds of work.
2A.4 Heat transactions
In general, the change in internal energy of a system is
dU = dq + dwexp + dwe (2A.10)
where dwe is work in addition (e for ‘extra’) to the expansion
work, dwexp. For instance, dwe might be the electrical work of
driving a current through a circuit. A system kept at constant
volume can do no expansion work, so dwexp = 0. If the system
is also incapable of doing any other kind of work (if it is not,
for instance, an electrochemical cell connected to an electric
motor), then dwe = 0 too. Under these circumstances:
dU = dq Heat transferred at constant volume (2A.11a)
We express this relation by writing dU = dqV , where the sub-
script implies a change at constant volume. For a measurable
change between states i and f along a path at constant volume,
U −U
 q

f i V
f f
∫ dU = ∫ dq
i i
which we summarize as
∆U = qV (2A.11b)
Note that we do not write the integral over dq as Δq because
q, unlike U, is not a state function. It follows that, by measur-
ing the energy supplied to a constant-volume system as heat
(qV > 0) or released from it as heat (qV < 0) when it undergoes a
change of state, we are in fact measuring the change in its inter-
nal energy.
(a) Calorimetry
Calorimetry is the study of the transfer of energy as heat dur-
ing physical and chemical processes. A calorimeter is a device
for measuring energy transferred as heat. The most common
device for measuring qV (and therefore ΔU) is an adiabatic
bomb calorimeter (Fig. 2A.8). The process we wish to study—
which may be a chemical reaction—is initiated inside a con-
stant-volume container, the ‘bomb’. The bomb is immersed in
72 2 The First Law
Firing
Thermometer
Oxygen input leads
Bomb
Sample
Oxygen
under pressure
Water
Figure 2A.8 A constant-volume bomb calorimeter. The ‘bomb’
is the central vessel, which is strong enough to withstand
high pressures. The calorimeter (for which the heat capacity
must be known) is the entire assembly shown here. To ensure
adiabaticity, the calorimeter is immersed in a water bath with a
temperature continuously readjusted to that of the calorimeter
at each stage of the combustion.
a stirred water bath, and the whole device is the calorimeter.
The calorimeter is also immersed in an outer water bath. The
water in the calorimeter and of the outer bath are both moni-
tored and adjusted to the same temperature. This arrangement
ensures that there is no net loss of heat from the calorimeter to
the surroundings (the bath) and hence that the calorimeter is
adiabatic.
The change in temperature, ΔT, of the calorimeter is propor-
tional to the energy that the reaction releases or absorbs as heat.
Therefore, by measuring ΔT we can determine qV and hence
find ΔU. The conversion of ΔT to qV is best achieved by cali-
brating the calorimeter using a process of known energy output
and determining the calorimeter constant, the constant C in
the relation
q = C∆T (2A.12)
The calorimeter constant may be measured electrically by pass-
ing a constant current, I, from a source of known potential dif-
ference, Δϕ, through a heater for a known period of time, t, for
then
q = It ∆φ (2A.13)
Electrical charge is measured in coulombs, C. The motion of
charge gives rise to an electric current, I, measured in cou-
lombs per second, or amperes, A, where 1 A = 1 C s−1. If a
constant current I flows through a potential difference Δϕ
(measured in volts, V), the total energy supplied in an interval
t is ItΔϕ. Because 1 A V s = 1 (C s−1) V s = 1 C V = 1 J, the energy
is obtained in joules with the current in amperes, the potential
difference in volts, and the time in seconds.
Brief illustration 2A.6 Electrical heating
If a current of 10.0 A from a 12 V supply is passed for 300 s,
then from eqn 2A.13 the energy supplied as heat is
q = (10.0 A) × (12 V) × (300 s) = 3.6 ×104 A Vs = 36 kJ
because 1 A V s = 1 J. If the observed rise in temperature is
5.5 K, then the calorimeter constant is C = (36 kJ)/(5.5 K) =
6.5 kJ K−1.
Self-test 2A.7 What is the value of the calorimeter constant if
the temperature rises by 4.8 °C when a current of 8.6 A from
an 11 V supply is passed for 280 s?
Answer: 5.5 kJ K−1
Alternatively, C may be determined by burning a known
mass of substance (benzoic acid is often used) that has a known
heat output. With C known, it is simple to interpret an observed
temperature rise as a release of heat.
(b) Heat capacity
The internal energy of a system increases when its temperature
is raised. The increase depends on the conditions under which
the heating takes place and for the present we suppose that the
system has a constant volume. For example, it may be a gas in
a container of fixed volume. If the internal energy is plotted
against temperature, then a curve like that in Fig. 2A.9 may be
obtained. The slope of the tangent to the curve at any tempera-
ture is called the heat capacity of the system at that tempera-
ture. The heat capacity at constant volume is denoted CV and is
defined formally as
Internal energy, U
B
A
Temperature, T
Figure 2A.9 The internal energy of a system increases as
the temperature is raised; this graph shows its variation as
the system is heated at constant volume. The slope of the
tangent to the curve at any temperature is the heat capacity at
constant volume at that temperature. Note that, for the system
illustrated, the heat capacity is greater at B than at A.
 2A Internal energy 73

substance, which is the heat capacity of the sample divided by

Internal energy, U
the mass, usually in grams: CV,s = CV/m. The specific heat capacity
Temperature variation of water at room temperature is close to 4.2 J K−1 g−1. In general,
of U Slope of U against T
heat capacities depend on the temperature and decrease at low
at constant V
temperatures. However, over small ranges of temperature at
and above room temperature, the variation is quite small and
for approximate calculations heat capacities can be treated as
almost independent of temperature.
The heat capacity is used to relate a change in internal energy
Temperature, T
to a change in temperature of a constant-volume system. It fol-
Volume, V
lows from eqn 2A.14 that

Figure 2A.10 The internal energy of a system varies with dU = CV dT Constant volume (2A.15a)
volume and temperature, perhaps as shown here by the
surface. The variation of the internal energy with temperature That is, at constant volume, an infinitesimal change in tempera­
at one particular constant volume is illustrated by the curve ture brings about an infinitesimal change in internal energy,
drawn parallel to T. The slope of this curve at any point is the
and the constant of proportionality is CV . If the heat capacity
partial derivative (∂U/∂T)V.
is independent of temperature over the range of temperatures
of interest, then
 ∂U 
CV =  (2A.14)
 ∂T  V
Definition Heat capacity at constant volume ∆T
 
T2 T2
∆U = ∫ T1
CV dT = CV ∫
T1
dT = CV (T2 − T1 )
Partial derivatives are reviewed in Mathematical background 2
following this chapter. The internal energy varies with the tem- and a measurable change of temperature, ΔT, brings about a
perature and the volume of the sample, but here we are inter- measurable change in internal energy, ΔU, where
ested only in its variation with the temperature, the volume
being held constant (Fig. 2A.10). ∆U = CV ∆T Constant volume (2A.15b)

Because a change in internal energy can be identified with the

Brief illustration 2A.7 Heat capacity heat supplied at constant volume (eqn 2A.11b), the last equa-
The heat capacity of a monatomic perfect gas can be calculated tion can also be written
by inserting the expression for the internal energy derived in
Brief illustration 2A.2 where we saw that U m (T ) = U m (0) + 23 RT , qV = CV ∆T (2A.16)
so from eqn 2A.14
This relation provides a simple way of measuring the heat
∂
CV ,m = {
U (0) + 23 RT = 23 R
∂T m
} capacity of a sample: a measured quantity of energy is trans-
ferred as heat to the sample (electrically, for example), and the
resulting increase in temperature is monitored. The ratio of
The numerical value is 12.47 J K−1 mol−1.
the energy transferred as heat to the temperature rise it causes
Self-test 2A.8 Estimate the molar constant-volume heat cap­ (qV/ΔT) is the constant-volume heat capacity of the sample.
acity of carbon dioxide.
Answer: 5
2
R = 21 J K −1 mol −1 Brief illustration 2A.8 The determination of a heat
capacity
Suppose a 55 W electric heater immersed in a gas in a con-
Heat capacities are extensive properties: 100 g of water, for
stant-volume adiabatic container was on for 120 s and it
instance, has 100 times the heat capacity of 1 g of water (and
was found that the temperature of the gas rose by 5.0 °C
therefore requires 100 times the energy as heat to bring about
(an increase equivalent to 5.0 K). The heat supplied is
the same rise in temperature). The molar heat capacity at con-
(55 W) × (120 s) = 6.6 kJ (we have used 1 J = 1 W s), so the heat
stant volume, CV,m = CV/n, is the heat capacity per mole of sub- capacity of the sample is
stance, and is an intensive property (all molar quantities are
intensive). Typical values of CV,m for polyatomic gases are close 6.6 kJ
CV = = 1.3 kJ K −1
to 25 J K−1 mol−1. For certain applications it is useful to know the 5. 0 K
specific heat capacity (more informally, the ‘specific heat’) of a
74 2 The First Law

infinite heat capacity implies that there will be no increase in

Self-test 2A.9 When 229 J of energy is supplied as heat to
3.0 mol of a gas at constant volume, the temperature of the gas
increases by 2.55 °C. Calculate CV and the molar heat capacity
at constant volume.
Answer: 89.8 J K−1, 29.9 J K−1 mol−1
A large heat capacity implies that, for a given quantity of
energy transferred as heat, there will be only a small increase
in temperature (the sample has a large capacity for heat). An
temperature however much energy is supplied as heat. At a
phase transition, such as at the boiling point of water, the tem-
perature of a substance does not rise as energy is supplied as
heat: the energy is used to drive the endothermic transition, in
this case to vaporize the water, rather than to increase its tem-
perature. Therefore, at the temperature of a phase transition,
the heat capacity of a sample is infinite. The properties of heat
capacities close to phase transitions are treated more fully in
Topic 4B.

Checklist of concepts
☐ 1. Work is done to achieve motion against an opposing ☐ 7. The First Law states that the internal energy of an iso-
force lated system is constant.
☐ 2. Energy is the capacity to do work. ☐ 8. Free expansion (expansion against zero pressure) does
☐ 3. Heating is the transfer of energy that makes use of dis- no work.
orderly molecular motion. ☐ 9. To achieve reversible expansion, the external pressure is
☐ 4. Work is the transfer of energy that makes use of organ- matched at every stage to the pressure of the system.
ized motion. ☐ 10. The energy transferred as heat at constant volume is
☐ 5. Internal energy, the total energy of a system, is a state equal to the change in internal energy of the system.
function. ☐ 11. Calorimetry is the measurement of heat transactions.
☐ 6. The equipartition theorem can be used to estimate the
contribution to the internal energy of classical modes of
motion.

Checklist of equations
Property Equation Comment Equation number

First Law of thermodynamics ΔU = q + w Acquisitive convention 2A.2

Work of expansion dw = −pexdV 2A.5a

Work of expansion against a constant external pressure w = −pexΔV pex = 0 corresponds to free expansion 2A.6

Reversible work of expansion of a gas w = −nRT ln(Vf/Vi) Isothermal, perfect gas 2A.9

Internal energy change ΔU = qV Constant volume, no other forms of work 2A.11b

Electrical heating q = ItΔϕ 2A.13

Heat capacity at constant volume CV = (∂U/∂T)V Definition 2A.14

2B Enthalpy

Contents
Energy as work
2B.1 The definition of enthalpy 75
(a) Enthalpy change and heat transfer 75
Brief illustration 2B.1: A change in enthalpy 76
(b) Calorimetry 76 ΔU < q

Example 2B.1: Relating ΔH and ΔU 77 Energy

as heat
Brief illustration 2B.2: Processes involving gases 77
2B.2 The variation of enthalpy with temperature 77
(a) Heat capacity at constant pressure 77
Example 2B.2: Evaluating an increase in enthalpy
with temperature 78 Figure 2B.1 When a system is subjected to constant pressure
(b) The relation between heat capacities 79 and is free to change its volume, some of the energy supplied
Checklist of concepts 79 as heat may escape back into the surroundings as work. In such
Checklist of equations 79 a case, the change in internal energy is smaller than the energy
supplied as heat.

2B.1 The definition of enthalpy

➤➤ Why do you need to know this material? The enthalpy, H, is defined as
The concept of enthalpy is central to many thermodynamic
discussions about processes taking place under conditions H = U + pV Definition Enthalpy (2B.1)
of constant pressure, such as the discussion of the heat
requirements or output of physical transformations and where p is the pressure of the system and V is its volume.
chemical reactions. Because U, p, and V are all state functions, the enthalpy is a
state function too. As is true of any state function, the change
➤➤ What is the key idea? in enthalpy, ΔH, between any pair of initial and final states is
A change in enthalpy is equal to the energy transferred as independent of the path between them.
heat at constant pressure.

➤➤ What do you need to know already? (a) Enthalpy change and heat transfer
This Topic makes use of the discussion of internal energy Although the definition of enthalpy may appear arbitrary, it has
(Topic 2A) and draws on some aspects of perfect gases important implications for thermochemistry. For instance, we
(Topic 1A). show in the following Justification that eqn 2B.1 implies that the
change in enthalpy is equal to the energy supplied as heat at con-
stant pressure (provided the system does no additional work):
The change in internal energy is not equal to the energy trans-
ferred as heat when the system is free to change its volume, dH = dq p Heat transferred at constant pressure (2B.2a)
such as when it is able to expand or contract under conditions
of constant pressure. Under these circumstances some of the For a measurable change between states i and f along a path at
energy supplied as heat to the system is returned to the sur- constant pressure, we write
roundings as expansion work (Fig. 2B.1), so dU is less than dq.
qp
In this case the energy supplied as heat at constant pressure is H −H
  f i

equal to the change in another thermodynamic property of the f f

system, the enthalpy. ∫ dH = ∫ dq

i i
p
76 2 The First Law
and summarize the result as
∆H = q p
Note that we do not write the integral over dq as Δq because q,
unlike H, is not a state function.
Brief illustration 2B.1 A change in enthalpy
Water is heated to boiling under a pressure of 1.0 atm. When an
electric current of 0.50 A from a 12 V supply is passed for 300 s
through a resistance in thermal contact with it, it is found that
0.798 g of water is vaporized. The enthalpy change is
∆H = q p = It ∆φ = (0.50 A) × (12 V) × (300 s) = ( 0.50 ×12 × 300) J
Here we have used 1 A V s = 1 J. Because 0.798 g of water is
(0.798 g)/(18.02 g mol−1) = (0.798/18.02) mol H2O, the enthalpy
of vaporization per mole of H2O is
(0.50 × 12 × 300)J
∆H m = = +41 kJmol −1
(0.798 /18.02) mol
Self-test 2B.1 The molar enthalpy of vaporization of benzene
at its boiling point (353.25 K) is 30.8 kJ mol−1. For how long
would the same 12 V source need to supply a 0.50 A current in
order to vaporize a 10 g sample?
Answer: 6.6 × 102 s
Justification 2B.1 The relation ΔH = qp
For a general infinitesimal change in the state of the system,
U changes to U + dU, p changes to p + dp, and V changes to
V + dV, so from the definition in eqn 2B.1, H changes from
U + pV to
H + dH = (U + dU ) + ( p + dp)(V + dV )
= U + dU + pV + pdV + Vdp + dpdV
The last term is the product of two infinitesimally small quanti-
ties and can therefore be neglected. As a result, after recogniz-
ing U + pV = H on the right (in blue), we find that H changes to
H + dH = H + dU + pdV + Vdp
and hence that
dH = dU + pdV + Vdp
If we now substitute dU = dq + dw into this expression, we get
dH = dq + dw + pdV + Vdp
If the system is in mechanical equilibrium with its surround-
ings at a pressure p and does only expansion work, we can
(2B.2b) write dw = −pdV and obtain
dH = dq + Vdp
Now we impose the condition that the heating occurs at con-
stant pressure by writing dp = 0. Then
dH = dq (at constant pressure, no additional work )
as in eqn 2B.2a. Equation 2B.2b then follows, as explained in
the text.
(b) Calorimetry
The process of measuring heat transactions between a system
and its surroundings is called calorimetry. An enthalpy change
can be measured calorimetrically by monitoring the tempera-
ture change that accompanies a physical or chemical change
occurring at constant pressure. A calorimeter for studying pro-
cesses at constant pressure is called an isobaric calori­meter.
A simple example is a thermally insulated vessel open to the
atmosphere: the heat released in the reaction is monitored by
measuring the change in temperature of the contents. For a
combustion reaction an adiabatic flame calorimeter may be
used to measure ΔT when a given amount of substance burns
in a supply of oxygen (Fig. 2B.2).
Another route to ΔH is to measure the internal energy
change by using a bomb calorimeter, and then to convert ΔU
to ΔH. Because solids and liquids have small molar volumes,
for them pVm is so small that the molar enthalpy and molar
internal energy are almost identical (Hm = Um + pVm ≈ Um).
Consequently, if a process involves only solids or liquids, the
values of ΔH and ΔU are almost identical. Physically, such pro-
cesses are accompanied by a very small change in volume; the
system does negligible work on the surroundings when the
process occurs, so the energy supplied as heat stays entirely
Gas, vapour
Oxygen
Products
Figure 2B.2 A constant-pressure flame calorimeter consists of
this component immersed in a stirred water bath. Combustion
occurs as a known amount of reactant is passed through to fuel
the flame, and the rise of temperature is monitored.

within the system. The most sophisticated way to measure
enthalpy changes, however, is to use a differential scanning calo-
rimeter (DSC), as explained in Topic 2C. Changes in enthalpy
and internal energy may also be measured by non-calorimetric
methods (see Topic 6C).
Example 2B.1 Relating ΔH and ΔU
The change in molar internal energy when CaCO3(s) as cal-
cite converts to another form, aragonite, is +0.21 kJ mol −1.
Calculate the difference between the molar enthalpy and
internal energy changes when the pressure is 1.0 bar given that
the densities of the polymorphs are 2.71 g cm−3 (calcite) and
2.93 g cm−3 (aragonite).
Method The starting point for the calculation is the rela-
tion between the enthalpy of a substance and its internal
energy (eqn 2B.1). The difference between the two quantities
can be expressed in terms of the pressure and the difference
of their molar volumes, and the latter can be calculated from
their molar masses, M, and their mass densities, ρ, by using
ρ = M/Vm.
Answer The change in enthalpy when the transition occurs is
∆H m = H m (aragonite) − H m (calcite)
= {U m (a ) + pVm (a)} − {U m (c) + pVm (c)}
= ∆U m + p {Vm (a ) − Vm (c)}
where a denotes aragonite and c calcite. It follows by substitut-
ing Vm = M/ρ that
 1 1 
∆H m − ∆U m = pM  −
 ρ (a ) ρ (c) 
Substitution of the data, using M = 100.09 g mol−1, gives
∆H m − ∆U m = (1.0 ×105 Pa) × (100.09 g mol −1 )
 1 1 
× −
 2.93 g cm −3
2.71 g cm −3 
 The variation of enthalpy with
= −2.8 ×105 Pacm3 mol −1 = −0.28 Pa m3 mol −1
Hence (because 1 Pa m3 = 1 J), ΔHm − ΔUm = –0.28 J mol−1, which
is only 0.1 per cent of the value of ΔUm. We see that it is usually
justifiable to ignore the difference between the molar enthalpy
and internal energy of condensed phases, except at very high
pressures, when pΔVm is no longer negligible.
Self-test 2B.2 Calculate the difference between ΔH and ΔU
when 1.0 mol Sn(s, grey) of density 5.75 g cm−3 changes to Sn(s,
white) of density 7.31 g cm−3 at 10.0 bar. At 298 K, ΔH = +2.1 kJ.
Answer: ΔH − ΔU = −4.4 J
2B Enthalpy 77
In contrast to processes involving condensed phases, the val-
ues of the changes in internal energy and enthalpy may differ
significantly for processes involving gases. Thus, the enthalpy of
a perfect gas is related to its internal energy by using pV = nRT
in the definition of H:
H = U + pV = U + nRT (2B.3)
This relation implies that the change of enthalpy in a reaction
that produces or consumes gas under isothermal conditions is
Relation
Perfect gas,
∆H = ∆U + ∆ng RT isothermal between ΔH (2B.4)
and ΔU
where Δng is the change in the amount of gas molecules in the
reaction.
Brief illustration 2B.2
Processes involving gases
In the reaction 2 H2(g) + O2(g) → 2 H2O(l), 3 mol of gas-phase
molecules are replaced by 2 mol of liquid-phase molecules, so
Δng = −3 mol. Therefore, at 298 K, when RT = 2.5 kJ mol−1, the
enthalpy and internal energy changes taking place in the sys-
tem are related by
∆H m − ∆U m = (−3 mol ) × RT ≈ −7.4 kJmol −1
Note that the difference is expressed in kilojoules, not joules
as in Example 2B.2. The enthalpy change is smaller (in this
case, less negative) than the change in internal energy because,
although heat escapes from the system when the reaction
occurs, the system contracts when the liquid is formed, so
energy is restored to it from the surroundings.
Self-test 2B.3 Calculate the value of ΔHm − ΔUm for the reac-
tion N2(g) + 3 H2(g) → 2 NH3(g).
Answer: –5.0 kJ mol−1
2B.2
temperature
The enthalpy of a substance increases as its temperature is
raised. The relation between the increase in enthalpy and the
increase in temperature depends on the conditions (for exam-
ple, constant pressure or constant volume).
(a) Heat capacity at constant pressure
The most important condition is constant pressure, and the
slope of the tangent to a plot of enthalpy against temperature
at constant pressure is called the heat capacity at constant
78 2 The First Law

Table 2B.1* Temperature variation of molar heat capacities,

Cp,m/(J K−1 mol−1) = a + bT + c/T 2
B a b/(10−3 K−1) c/(105 K2)
Enthalpy, H

C(s, graphite) 16.86 4.77 −8.54

CO2(g) 44.22 8.79 −8.62
Internal
H2O(l) 75.29 0 0
A energy, U
N2(g) 28.58 3.77 −0.50
* More values are given in the Resource section.

Temperature, T
This expression shows us how to measure the heat capacity of a
Figure 2B.3 The constant-pressure heat capacity at a sample: a measured quantity of energy is supplied as heat under
particular temperature is the slope of the tangent to a curve conditions of constant pressure (as in a sample exposed to the
of the enthalpy of a system plotted against temperature (at atmosphere and free to expand), and the temperature rise is
constant pressure). For gases, at a given temperature the slope monitored.
of enthalpy versus temperature is steeper than that of internal The variation of heat capacity with temperature can some-
energy versus temperature, and Cp,m is larger than CV,m. times be ignored if the temperature range is small; this approxi-
mation is highly accurate for a monatomic perfect gas (for
pressure (or isobaric heat capacity), Cp, at a given temperature instance, one of the noble gases at low pressure). However,
(Fig. 2B.3). More formally: when it is necessary to take the variation into account, a con-
venient approximate empirical expression is
 ∂H  c
Cp =  Definition (2B.5) C p,m = a + bT + (2B.8)
 ∂T  p
Heat capacity at constant pressure
T2
The empirical parameters a, b, and c are independent of tem-
The heat capacity at constant pressure is the analogue of the perature (Table 2B.1) and are found by fitting this expression to
heat capacity at constant volume (Topic 1A) and is an exten- experimental data.
sive property. The molar heat capacity at constant pressure,
Cp,m, is the heat capacity per mole of substance; it is an intensive Example 2B.2 Evaluating an increase in enthalpy
property. with temperature
The heat capacity at constant pressure is used to relate the
change in enthalpy to a change in temperature. For infinitesi- What is the change in molar enthalpy of N2 when it is heated
mal changes of temperature, from 25 °C to 100 °C? Use the heat capacity information in
Table 2B.1.
dH = C p dT (at constant pressure) (2B.6a) Method The heat capacity of N2 changes with temperature, so
we cannot use eqn 2B.6b (which assumes that the heat capac-
If the heat capacity is constant over the range of temperatures of ity of the substance is constant). Therefore, we must use eqn
interest, then for a measurable increase in temperature 2B.6a, substitute eqn 2B.8 for the temperature dependence of
the heat capacity, and integrate the resulting expression from
T2 T2 ∆T
  25 °C (298 K) to 100 °C (373 K).
∆H = ∫T1
C p dT = C p ∫
T1
dT = C p (T2 − T1 )
Answer For convenience, we denote the two temperatures T1
(298 K) and T2 (373 K). The relation we require is
which we can summarize as
H m (T2 ) T2
 c 
∆H = C p ∆T (at constant pressure) (2B.6b) ∫ H m (T1 )
dH m = ∫T1
 a + bT + T 2  dT

Because a change in enthalpy can be equated with the energy After using Integral A.1 in the Resource section, it follows that
supplied as heat at constant pressure, the practical form of the
latter equation is  1 1
H m (T2 ) − H m (T1 ) = a(T2 − T1 ) + 12 b(T22 − T12 ) − c  − 
 T2 T1 
q p = C p ∆T (2B.7)
 2B Enthalpy 79

energy supplied to them as heat escapes back to the surround-

Substitution of the numerical data results in
H m (373 K ) = H m (298 K ) + 2.20 kJmol −1
If we had assumed a constant heat capacity of 29.14 J K−1 mol−1
(the value given by eqn 2B.8 for T = 298 K), we would have
found that the two enthalpies differed by 2.19 kJ mol−1.
Self-test 2B.4 At very low temperatures the heat capacity of a
solid is proportional to T3, and we can write Cp,m = aT3. What
is the change in enthalpy of such a substance when it is heated
from 0 to a temperature T (with T close to 0)?
Answer: ∆H m = 14 aT 4
(b) The relation between heat capacities
Most systems expand when heated at constant pressure. Such
systems do work on the surroundings and therefore some of the
ings. As a result, the temperature of the system rises less than
when the heating occurs at constant volume. A smaller increase
in temperature implies a larger heat capacity, so we conclude
that in most cases the heat capacity at constant pressure of a
system is larger than its heat capacity at constant volume. We
show in Topic 2D that there is a simple relation between the
two heat capacities of a perfect gas:
C p − CV = nR Perfect Relation between
gas heat capacities (2B.9)
It follows that the molar heat capacity of a perfect gas is about
8 J K−1 mol−1 larger at constant pressure than at constant vol-
ume. Because the molar constant-volume heat capacity of a
monatomic gas is about 23 R = 12 JK −1 mol −1, the difference is
highly significant and must be taken into account.

Checklist of concepts
☐ 1. Energy transferred as heat at constant pressure is equal ☐ 3. The heat capacity at constant pressure is equal to the
to the change in enthalpy of a system. slope of enthalpy with temperature.
☐ 2. Enthalpy changes are measured in a constant-pressure
calorimeter.

Checklist of equations
Property Equation Comment Equation number

Enthalpy H = U + pV Definition 2B.1

Heat transfer at constant pressure dH = dqp, No additional work 2B.2

ΔH = qp

Relation between ΔH and ΔU ΔH = ΔU + ΔngRT Molar volumes of the participating condensed 2B.4
phases are negligible; isothermal process

Heat capacity at constant pressure Cp = (∂H/∂T)p Definition 2B.5

Relation between heat capacities Cp – CV = nR Perfect gas 2B.9

2C Thermochemistry

Contents ➤➤ What do you need to know already?

2C.1 Standard enthalpy changes 80 You need to be aware of the definition of enthalpy and
(a) Enthalpies of physical change 81 its status as a state function (Topic 2B). The material on
Brief illustration 2C.1: A Born–Haber cycle 82 temperature dependence of reaction enthalpies makes
(b) Enthalpies of chemical change 82 use of information on heat capacity (Topic 2B).
Brief illustration 2C.2: Enthalpy of
combustion 83
(c) Hess’s law 83
Example 2C.1: Using Hess’s law 84 The study of the energy transferred as heat during the
2C.2 Standard enthalpies of formation 84 course of chemical reactions is called thermochemistry.
Brief illustration 2C.3: Enthalpies of formation of ions Thermochemistry is a branch of thermodynamics because a
in solution 85 reaction vessel and its contents form a system, and chemical
(a) The reaction enthalpy in terms of enthalpies reactions result in the exchange of energy between the system
of formation 85 and the surroundings. Thus we can use calorimetry to meas-
Brief illustration 2C.4: Enthalpies of formation 85 ure the energy supplied or discarded as heat by a reaction, and
(b) Enthalpies of formation and molecular can identify q with a change in internal energy if the reaction
modelling 85 occurs at constant volume or with a change in enthalpy if the
Brief illustration 2C.5: Molecular modelling 86 reaction occurs at constant pressure. Conversely, if we know
2C.3 The temperature dependence of reaction ΔU or ΔH for a reaction, we can predict the heat the reaction
enthalpies 86 can produce.
Example 2C.2: Using Kirchhoff’s law 87 As pointed out in Topic 2A, a process that releases energy as
2C.4 Experimental techniques 87 heat into the surroundings is classified as exothermic and one
(a) Differential scanning calorimetry 87 that absorbs energy as heat from the surroundings is classified
(b) Isothermal titration calorimetry 88 as endothermic. Because the release of heat at constant pres-
Checklist of concepts 88 sure signifies a decrease in the enthalpy of a system, it follows
Checklist of equations 89 that an exothermic process is one for which ΔH < 0. Conversely,
because the absorption of heat results in an increase in enthalpy,
an endothermic process has ΔH > 0:
exothermic process : ∆H < 0 endothermic process : ∆H > 0

➤➤ Why do you need to know this material?

Thermochemistry is one of the principal applications of
thermodynamics in chemistry, for thermochemical data
provide a way of assessing the heat output of chemical
reactions, including those involved in the consumption
of fuels and foods. The data are also used widely in other
chemical applications of thermodynamics.
➤➤ What is the key idea?
2C.1 Standard enthalpy changes
Changes in enthalpy are normally reported for processes taking
place under a set of standard conditions. In most of our discus-
sions we shall consider the standard enthalpy change, ΔH<,
the change in enthalpy for a process in which the initial and
final substances are in their standard states:
Specification
of standard

Reaction enthalpies can be combined to provide data on The standard state of a substance at a specified
other reactions of interest. temperature is its pure form at 1 bar.
state
 2c Thermochemistry 81

For example, the standard state of liquid ethanol at 298 K is Table 2C.2 Enthalpies of transition
pure liquid ethanol at 298 K and 1 bar; the standard state of
Transition Process Symbol*
solid iron at 500 K is pure iron at 500 K and 1 bar. The defini-
Transition Phase α → phase β ΔtrsH
tion of standard state is more sophisticated for solutions (Topic
5E). The standard enthalpy change for a reaction or a physical Fusion s→l ΔfusH
process is the difference between the products in their standard Vaporization l→g ΔvapH
states and the reactants in their standard states, all at the same Sublimation s→g ΔsubH
specified temperature. Mixing Pure → mixture ΔmixH
As an example of a standard enthalpy change, the standard Solution Solute → solution ΔsolH
enthalpy of vaporization, ΔvapH<, is the enthalpy change per Hydration X±(g) → X±(aq) ΔhydH
mole of molecules when a pure liquid at 1 bar vaporizes to a gas
Atomization Species(s, l, g) → atoms(g) ΔatH
at 1 bar, as in
Ionization X(g) → X+(g) + e−(g) ΔionH
Electron gain X(g) + e−(g) → X−(g) ΔegH
H2 O(l) → H2 O(g) ∆ vap H < (373 K) = + 40.66 kJmol −1
Reaction Reactants → products ΔrH
As implied by the examples, standard enthalpies may be Combustion Compound(s, l, g) + O2(g) → CO2(g), ΔcH
H2O(l, g)
reported for any temperature. However, the conventional tem-
perature for reporting thermodynamic data is 298.15 K. Unless Formation Elements → compound ΔfH
otherwise mentioned or indicated by attaching the temperature Activation Reactants → activated complex Δ ‡H
to ΔH<, all thermodynamic data in this text are for this con- * IUPAC recommendations. In common usage, the transition subscript is often
ventional temperature. attached to ΔH, as in ΔHtrs.

A note on good practice The attachment of the name of the

transition to the symbol Δ, as in ΔvapH, is the current con-
vention. However, the older convention, ΔHvap, is still widely
used. The current convention is more logical because the sub-
script identifies the type of change, not the physical observ-
able related to the change.
(a) Enthalpies of physical change
The standard enthalpy change that accompanies a change
of physical state is called the standard enthalpy of transi-
tion and is denoted ΔtrsH< (Table 2C.1). The standard
enthalpy of vaporization, Δ vapH<, is one example. Another
is the standard enthalpy of fusion, ΔfusH<, the standard
enthalpy change accompanying the conversion of a solid to
a liquid, as in
H2 O(s) → H2 O(l) ∆ fus H < (273 K ) = + 6.01kJmol −1
As in this case, it is sometimes convenient to know the stand-
ard enthalpy change at the transition temperature as well as at
the conventional temperature of 298 K. The different types of
enthalpies encountered in thermochemistry are summarized in
Table 2C.2. We meet them again in various locations through-
out the text.
Because enthalpy is a state function, a change in enthalpy is
independent of the path between the two states. This feature
is of great importance in thermochemistry, for it implies that
the same value of ΔH< will be obtained however the change
is brought about between the same initial and final states. For
example, we can picture the conversion of a solid to a vapour
either as occurring by sublimation (the direct conversion from
solid to vapour),
H2 O(s) → H2 O(g) ∆ sub H <
or as occurring in two steps, first fusion (melting) and then
vaporization of the resulting liquid:

Table 2C.1* Standard enthalpies of fusion and vaporization at H2 O(s) → H2 O(l) ∆ fus H <
the transition temperature, ΔtrsH < /(kJ mol−1) H2 O(l) → H2 O(g) ∆ vap H <
Tf/K Fusion Tb/K Vaporization Overall : H2 O(s) → H2 O(g) ∆ fus H < + ∆ vap H <
Ar 83.81 1.188 87.29 6.506 Because the overall result of the indirect path is the same as that
C6H6 278.61 10.59 353.2 30.8 of the direct path, the overall enthalpy change is the same in
H2O 273.15 6.008 373.15 40.656 (44.016 each case (1), and we can conclude that (for processes occur-
at 298 K)
ring at the same temperature)
He 3.5 0.021 4.22 0.084
∆ sub H < = ∆ fus H < + ∆ vap H < (2C.1)
* More values are given in the Resource section.
82 2 The First Law

An immediate conclusion is that, because all enthalpies of

K+(g) + e–(g) + Cl(g)
fusion are positive, the enthalpy of sublimation of a sub-
stance is greater than its enthalpy of vaporization (at a given +418 –349
temperature).
K+(g) + Cl–(g)
K(g) + Cl(g)

Enthalpy
+122
g K(g) + ½ Cl2(g)
+89
K(s) + ½ Cl2(g) –ΔHL
Enthalpy, H

ΔvapH <
1 ΔsubH < +437
l
KCl(s)
ΔfusH <
s
Figure 2C.1 The Born–Haber cycle for KCl at 298 K. Enthalpy
Another consequence of H being a state function is that the changes are in kilojoules per mole.
standard enthalpy changes of a forward process and its reverse
differ in sign (2): It consists of the following steps (for convenience, starting at
the elements):
∆H <(A → B) = − ∆H <(B → A) (2C.2)
ΔH</(kJ mol−1)
1. Sublimation of K(s) +89 [dissociation enthalpy
For instance, because the enthalpy of vaporization of water is of K(s)]
+44 kJ mol−1 at 298 K, its enthalpy of condensation at that tem- 2. Dissociation of +122 [ 12 × dissociation
perature is −44 kJ mol−1. 1 Cl (g )
2 2 enthalpy of Cl2(g)]
3. Ionization of K(g) +418 [ionization enthalpy
of K(g)]
B
4. Electron attachment –349 [electron gain
Enthalpy, H

ΔH <(A→B)

ΔH <(B→A)

to Cl(g) enthalpy of Cl(g)]

2 5. Formation of solid –ΔHL/(kJ mol−1)
from gas
A 6. Decomposition of +437 [negative of enthalpy
compound of formation of
KCl(s)]
The vaporization of a solid often involves a large increase
Because the sum of these enthalpy changes is equal to zero, we
in energy, especially when the solid is ionic and the strong
can infer from
Coulombic interaction of the ions must be overcome in a pro-
cess such as 89 + 122 + 418 − 349 − ∆H L /(kJmol −1 ) + 437 = 0

MX(s) → M + (g ) + X − (g ) that ΔHL = +717 kJ mol−1.

The lattice enthalpy, ΔHL, is the change in standard molar
enthalpy for this process. The lattice enthalpy is equal to the
lattice internal energy at T = 0; at normal temperatures they
differ by only a few kilojoules per mole, and the difference is
normally neglected.
Experimental values of the lattice enthalpy are obtained by
using a Born–Haber cycle, a closed path of transformations
starting and ending at the same point, one step of which is the
formation of the solid compound from a gas of widely sepa-
rated ions.
Self-test 2C.1 Assemble a similar cycle for the lattice enthalpy
of magnesium chloride.
Answer: 2523 kJ mol−1
Lattice enthalpies obtained in the same way as in Brief illustra-
tion 2C.1 are listed in Table 2C.3. They are large when the ions
are highly charged and small, for then they are close together
and attract each other strongly. We examine the quantitative
relation between lattice enthalpy and structure in Topic 18B.

Brief illustration 2C.1 A Born–Haber cycle (b) Enthalpies of chemical change

A typical Born–Haber cycle, for potassium chloride, is shown Now we consider enthalpy changes that accompany chemi-
in Fig. 2C.1. cal reactions. There are two ways of reporting the change in
enthalpy that accompanies a chemical reaction. One is to write
 2c Thermochemistry 83

Table 2C.3* Lattice enthalpies at 298 K, ΔHL/(kJ mol−1) because the absolute values of the standard molar enthalpies are
unknown: we see in Section 2C.2a how that problem is overcome.
NaF 787 Some standard reaction enthalpies have special names and
NaBr 751 a particular significance. For instance, the standard enthalpy
MgO 3850 of combustion, ΔcH<, is the standard reaction enthalpy for the
MgS 3406 complete oxidation of an organic compound to CO2 gas and
* More values are given in the Resource section.
liquid H2O if the compound contains C, H, and O, and to N2
gas if N is also present.
the thermochemical equation, a combination of a chemical
equation and the corresponding change in standard enthalpy:
Brief illustration 2C.2 Enthalpy of combustion
CH 4 (g ) + 2 O2 (g ) → CO2 (g ) + 2 H2 O(g) ∆H = −890 kJ <
The combustion of glucose is

ΔH< is the change in enthalpy when reactants in their standard C 6H12O6 (s) + 6 O2 (g ) → 6 CO2 (g ) + 6 H2O(l)
states change to products in their standard states: ∆ c H < = −2808 kJmol −1

Pure, separate reactants in their standard states The value quoted shows that 2808 kJ of heat is released when
→ pure, separate products in their standard states 1 mol C 6H12O 6 burns under standard conditions (at 298 K).
More values are given in Table 2C.4.
Except in the case of ionic reactions in solution, the enthalpy
Self-test 2C.2 Predict the heat output of the combustion of
changes accompanying mixing and separation are insignifi- 1.0 dm3 of octane at 298 K. Its mass density is 0.703 g cm−3.
cant in comparison with the contribution from the reaction
Answer: 34 MJ
itself. For the combustion of methane, the standard value
refers to the reaction in which 1 mol CH4 in the form of pure
methane gas at 1 bar reacts completely with 2 mol O2 in the
form of pure oxygen gas to produce 1 mol CO2 as pure carbon Table 2C.4* Standard enthalpies of formation (ΔfH < ) and
dioxide at 1 bar and 2 mol H2O as pure liquid water at 1 bar; combustion (ΔcH < ) of organic compounds at 298 K
the numerical value is for the reaction at 298.15 K. ΔfH</(kJ mol−1) ΔcH</(kJ mol−1)
Alternatively, we write the chemical equation and then report
Benzene, C6H6(l) +49.0 −3268
the standard reaction enthalpy, ΔrH< (or ‘standard enthalpy of
Ethane, C2H6(g) −84.7 −1560
reaction’). Thus, for the combustion of methane, we write
Glucose, C6H12O6(s) −1274 −2808

CH 4 (g ) + 2 O2 (g ) → CO2 (g ) + 2 H2 O(g) Methane, CH4(g) −74.8 −890

∆ r H < = −890 kJmol −1 Methanol, CH3OH(l) −238.7 −721

* More values are given in the Resource section.
For a reaction of the form 2 A + B → 3 C + D the standard reac-
tion enthalpy would be
(c) Hess’s law
∆ r H < = {3H m< (C) + H m< (D)} − {2H m< (A) + H m< (B)} Standard enthalpies of individual reactions can be combined to
obtain the enthalpy of another reaction. This application of the
where H m< (J) is the standard molar enthalpy of species J at the First Law is called Hess’s law:
temperature of interest. Note how the ‘per mole’ of ΔrH< comes
The standard enthalpy of an overall reaction is the
Hess’s law

directly from the fact that molar enthalpies appear in this

sum of the standard enthalpies of the individual
expression. We interpret the ‘per mole’ by noting the stoichio-
reactions into which a reaction may be divided.
metric coefficients in the chemical equation. In this case, ‘per
mole’ in ΔrH< means ‘per 2 mol A’, ‘per mole B’, ‘per 3 mol C’, or The individual steps need not be realizable in practice: they
‘per mol D’. In general, may be hypothetical reactions, the only requirement being
Standard that their chemical equations should balance. The thermody-
∆r H < = ∑
Products
H m< − ∑
Reactants
H m< Definition reaction
enthalpy
(2C.3) namic basis of the law is the path-independence of the value
of ΔrH< and the implication that we may take the specified
where in each case the molar enthalpies of the species are mul- reactants, pass through any (possibly hypothetical) set of
tiplied by their (dimensionless and positive) stoichiometric reactions to the specified products, and overall obtain the
coefficients, ν. This formal definition is of little practical value same change of enthalpy. The importance of Hess’s law is that
84 2 The First Law

information about a reaction of interest, which may be dif- The reference state of an element is its most

Specification
of reference
ficult to determine directly, can be assembled from informa- stable state at the specified temperature and
tion on other reactions. 1 bar.

state
For example, at 298 K the reference state of nitrogen is a gas of
Example 2C.1 N2 molecules, that of mercury is liquid mercury, that of carbon
Using Hess’s law
is graphite, and that of tin is the white (metallic) form. There is
The standard reaction enthalpy for the hydrogenation of one exception to this general prescription of reference states:
propene, the reference state of phosphorus is taken to be white phospho-
CH2aCHCH3 (g ) + H2 (g ) → CH3CH2CH3 (g ) rus despite this allotrope not being the most stable form but
simply the more reproducible form of the element. Standard
is −124 kJ mol−1. The standard reaction enthalpy for the com- enthalpies of formation are expressed as enthalpies per mole of
bustion of propane, molecules or (for ionic substances) formula units of the com-
pound. The standard enthalpy of formation of liquid benzene at
CH3CH2CH3 (g ) + 5 O2 (g) → 3 CO2 (g) + 4 H2O(l) 298 K, for example, refers to the reaction
is −2220 kJ mol−1. The standard reaction enthalpy for the for-
6 C(s, graphite) + 3 H2 (g ) → C 6 H6 (l)
mation of water,
H2 (g ) + 12 O2 (g ) → H2O(l) and is +49.0 kJ mol−1. The standard enthalpies of formation
of elements in their reference states are zero at all tempera-
is –286 kJ mol−1. Calculate the standard enthalpy of combus- tures because they are the enthalpies of such ‘null’ reactions
tion of propene. as N2(g) → N2(g). Some enthalpies of formation are listed in
Method The skill to develop is the ability to assemble a given Tables 2C.5 and 2C.6.
thermochemical equation from others. Add or subtract the The standard enthalpy of formation of ions in solution poses
reactions given, together with any others needed, so as to a special problem because it is impossible to prepare a solution
reproduce the reaction required. Then add or subtract the of cations alone or of anions alone. This problem is solved by
reaction enthalpies in the same way.
Answer The combustion reaction we require is Table 2C.5* Standard enthalpies of formation of inorganic
compounds at 298 K, ΔfH < /(kJ mol−1)
C 3H6 (g ) + 92 O2 (g ) → 3 CO2 (g ) + 3 H2O(l)
ΔfH</(kJ mol−1)
This reaction can be recreated from the following sum: H2O(l) −285.83
H2O(g) −241.82
ΔrH</(kJ mol−1)
NH3(g) −46.11
C3H6(g) + H2(g) → C3H8(g) −124
N2H4(l) +50.63
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) −2220
NO2(g) +33.18
H2O(l) → H2 (g ) + 12 O2 (g ) +286
9
N2O4(g) +9.16
C3H6 (g ) + 2
O2 (g ) → 3 CO2 (g ) + 3 H2O(l) −2058
NaCl(s) −411.15
Self-test 2C.3 Calculate the enthalpy of hydrogenation of KCl(s) −436.75
benzene from its enthalpy of combustion and the enthalpy of * More values are given in the Resource section.
combustion of cyclohexane.
Answer: −206 kJ mol−1 Table 2C.6* Standard enthalpies of formation of organic
compounds at 298 K, ΔfH < /(kJ mol−1)

ΔfH</(kJ mol−1)

Standard enthalpies of
2C.2 CH4(g) –74.81

formation C6H6(l) +49.0

C6H12(l) –156

The standard enthalpy of formation, ΔfH<, of a substance is CH3OH(l) –238.66

the standard reaction enthalpy for the formation of the com- CH3CH2OH(l) –277.69
pound from its elements in their reference states: * More values are given in the Resource section.
 2c Thermochemistry 85

defining one ion, conventionally the hydrogen ion, to have zero the same result is to introduce the stoichiometric numbers νJ
standard enthalpy of formation at all temperatures: (as distinct from the stoichiometric coefficients), which are
positive for products and negative for reactants. Then we can
∆ f H < (H + , aq ) = 0 Convention
Ions in
(2C.4)
write
solution

∆r H < = ∑ ∆ H
J
J f
<
(J) (2C.5b)

Brief illustration 2C.3 Enthalpies of formation of ions

in solution Stoichiometric numbers, which have a sign, are denoted νJ or
If the enthalpy of formation of HBr(aq) is found to be −122 kJ ν(J). Stoichiometric coefficients, which are all positive, are
mol−1, then the whole of that value is ascribed to the forma- denoted simply ν (with no subscript).
tion of Br− (aq), and we write Δ f H < (Br− ,aq) = −122 kJ mol−1.
That value may then be combined with, for instance, the Brief illustration 2C.4 Enthalpies of formation
enthalpy of formation of AgBr(aq) to determine the value of
Δ f H < (Ag+,aq), and so on. In essence, this definition adjusts According to eqn 2C.5a, the standard enthalpy of the reaction
the actual values of the enthalpies of formation of ions by a 2 HN3(l) + 2 NO(g) → H2O2(l) + 4 N2(g) is calculated as follows:
fixed amount, which is chosen so that the standard value for
one of them, H+(aq), has the value zero. ∆r H < = {∆ f H < (H2O2 , l ) + 4 ∆f H < (N2 , g )}
− {2 ∆f H < (HN3 , l) + 2 ∆f H < (NO, g )}
Self-test 2C.4 Determine the value of Δ f H < (Ag + ,aq); the
standard enthalpy of formation of AgBr(aq) is –17 kJ mol−1. = {−187.78 + 4(0)} kJmol −1 − {2(264.0)
Answer: +105 kJ mol−1 + 2(90.25)} kJmol −1
= −896.3 kJJ mol −1

To use eqn 2C.5b, we identify ν(HN3) = –2, ν(NO) = –2,

ν(H2O2) = +1, and ν(N2) = +4, and then write
(a) The reaction enthalpy in terms of
enthalpies of formation ∆ r H < = ∆ f H < (H2O2 , l) + 4 ∆ f H < (N2 , g ) − 2∆ f H < (HN3 , l)
− 2∆ f H < (NO, g )}
Conceptually, we can regard a reaction as proceeding by decom- which gives the same result.
posing the reactants into their elements and then forming those
elements into the products. The value of ΔrH< for the overall Self-test 2C.5 Evaluate the standard enthalpy of the reaction
reaction is the sum of these ‘unforming’ and forming enthalpies. C(graphite) + H2O(g) → CO(g) + H2(g).
Because ‘unforming’ is the reverse of forming, the enthalpy of an Answer: +131.29 kJ mol−1
unforming step is the negative of the enthalpy of formation (3).

Elements
Enthalpies of formation and molecular
(b)
Enthalpy, H

Reactants
modelling
3
ΔrH < We have seen how to construct standard reaction enthalpies by
Products combining standard enthalpies of formation. The question that
now arises is whether we can construct standard enthalpies of
Hence, in the enthalpies of formation of substances, we have formation from a knowledge of the chemical constitution of the
enough information to calculate the enthalpy of any reaction species. The short answer is that there is no thermodynamically
by using exact way of expressing enthalpies of formation in terms of con-
tributions from individual atoms and bonds. In the past, approx-
∆r H < = ∑ ∆ H
Products
f
<

Practical
Standard imate procedures based on mean bond enthalpies, ΔH(AeB),
reaction (2C.5a) the average enthalpy change associated with the breaking of a
− ∑ ∆ H
implementation
< enthalpy
f specific AeB bond,
Reactants

where in each case the enthalpies of formation of the species AeB(g )→ A(g) + B(g) ∆H (AeB)
that occur are multiplied by their stoichiometric coefficients.
This procedure is the practical implementation of the formal have been used. However, this procedure is notoriously unre-
definition in eqn 2C.3. A more sophisticated way of expressing liable, in part because the ΔH(AeB) are average values for a
86 2 The First Law

series of related compounds. Nor does the approach distinguish

between geometrical isomers, where the same atoms and bonds
may be present but experimentally the enthalpies of formation
might be significantly different. Products ΔrH <(T2)

Computer-aided molecular modelling has largely displaced
this more primitive approach. Commercial software pack-
ages use the principles developed in Topic 10E to calculate the
standard enthalpy of formation of a molecule drawn on the
computer screen. These techniques can be applied to different
conformations of the same molecule. In the case of methylcy-
clohexane, for instance, the calculated conformational energy
difference ranges from 5.9 to 7.9 kJ mol−1, with the equatorial
conformer having the lower standard enthalpy of formation.
These estimates compare favourably with the experimental
value of 7.5 kJ mol−1. However, good agreement between calcu-
lated and experimental values is relatively rare. Computational
methods almost always predict correctly which conformer is
more stable but do not always predict the correct magnitude of
the conformational energy difference. The most reliable tech-
nique for the determination of enthalpies of formation remains
calorimetry, typically by using enthalpies of combustion.
Enthalpy, H
ΔrH <(T1)
Reactants
T1
Temperature, T
T2
Figure 2C.2 When the temperature is increased, the enthalpy
of the products and the reactants both increase, but may do
so to different extents. In each case, the change in enthalpy
depends on the heat capacities of the substances. The change
in reaction enthalpy reflects the difference in the changes of
the enthalpies.
It follows from eqn 2B.6a (dH = CpdT) that, when a substance
is heated from T1 to T2, its enthalpy changes from H(T1) to

T2
Brief illustration 2C.5 Molecular modelling H (T2 ) = H (T2 ) + ∫ T1
C p dT (2C.6)

Each software package has its own procedures; the general

approach, though, is the same in most cases: the structure
of the molecule is specified and the nature of the calcula-
tion selected. When the procedure is applied to the axial and
equatorial isomers of methylcyclohexane, a typical value for
the standard enthalpy of formation of equatorial isomer in
the gas phase is –183 kJ mol−1 (using the AM1 semi-empirical
(We have assumed that no phase transition takes place in the
temperature range of interest.) Because this equation applies to
each substance in the reaction, the standard reaction enthalpy
changes from ΔrH<(T1) to
T2

procedure) whereas that for the axial isomer is –177 kJ mol−1, ∆ r H < (T2 ) = ∆ r H < (T2 ) + ∫ T1
∆ r C p< dT Kirchhoff’s law (2C.7a)
a difference of 6 kJ mol−1. The experimental difference is 7.5 kJ
mol−1.
where ∆ r C p< is the difference of the molar heat capacities of
Self-test 2C.6 If you have access to modelling software, repeat products and reactants under standard conditions weighted
this calculation for the two isomers of cyclohexanol. by the stoichiometric coefficients that appear in the chemical
Answer: Using AM1: eq: –345 kJ mol−1; ax: –349 kJ mol−1 equation:

∆ rC p<,m = ∑ C p<,m − ∑ C p<,m (2C.7b)

2C.3The temperature dependence of Products Reactants

reaction enthalpies or, in the notation of eqn 2C.5b,

The standard enthalpies of many important reactions have

been measured at different temperatures. However, in the
∆ rC p<,m = ∑ C
J
J
<
p ,m (J) (2C.7c)

absence of this information, standard reaction enthalpies at

different temperatures may be calculated from heat capaci-
ties and the reaction enthalpy at some other temperature (Fig.
2C.2). In many cases heat capacity data are more accurate than
reaction enthalpies. Therefore, providing the information is
available, the procedure we are about to describe is more accu-
rate than the direct measurement of a reaction enthalpy at an
elevated temperature.
Equation 2C.7a is known as Kirchhoff ’s law. It is normally
a good approximation to assume that ∆ r C p< is independent
of the temperature, at least over reasonably limited ranges.
Although the individual heat capacities may vary, their dif-
ference varies less significantly. In some cases the temperature
dependence of heat capacities is taken into account by using
eqn 2B.8.

Example 2C.2
Using Kirchhoff’s law
The standard enthalpy of formation of H 2O(g) at 298 K is
−241.82 kJ mol−1. Estimate its value at 100 °C given the fol-
lowing values of the molar heat capacities at constant pres-
sure: H 2O(g): 33.58 J K−1 mol−1; H2(g): 28.84 J K−1 mol−1; O2(g):
29.37 J −1 mol−1. Assume that the heat capacities are independ-
ent of temperature.
Method When ∆ r C p< is independent of temperature in
the range T1 to T 2 , the integral in eqn 2C.7a evaluates to
(T2 − T1 ) ∆ rC p< . Therefore,
∆ r H < (T2 ) = ∆ r H < (T1 ) + (T2 − T1 )∆ rC p<
To proceed, write the chemical equation, identify the stoichio-
metric coefficients, and calculate ∆ r C p< from the data.
Answer The reaction is H2 (g ) + 12 O2 (g ) → H2O(g ) , so
{ }
∆ rC p< = C p<,m (H2O, g ) − C p<,m (H2 , g ) + 12 C p<,m (O2 , g )
= −9.94 JK mol
−1 −1
It then follows that
∆ r H < (373 K ) = −241.82 kJmol −1 + (75 K )
× (−9.94 JK −1 mol −1 ) = −242.6 kJmol −1
Self-test 2C.7 Estimate the standard enthalpy of formation of
cyclohexane, C6H12(l), at 400 K from the data in Table 2C.6.
Answer: −163 kJ mol−1
2C.4 Experimental techniques
The classic tool of thermochemistry is the calorimeter, as sum-
marized in Topic 2B. However, technological advances have
been made that allow measurements to be made on samples
with mass as little as a few milligrams. We describe two of them
here.
(a) Differential scanning calorimetry
A differential scanning calorimeter (DSC) measures the
energy transferred as heat to or from a sample at constant
pressure during a physical or chemical change. The term ‘dif-
ferential’ refers to the fact that the behaviour of the sample is
compared to that of a reference material that does not undergo
a physical or chemical change during the analysis. The term
‘scanning’ refers to the fact that the temperatures of the sam-
ple and reference material are increased, or scanned, during the
analysis.
A DSC consists of two small compartments that are heated
electrically at a constant rate. The temperature, T, at time t dur-
ing a linear scan is T = T0 + αt, where T0 is the initial temperature
2c Thermochemistry 87
Thermocouples
Sample Reference
Heaters
Figure 2C.3 A differential scanning calorimeter. The sample
and a reference material are heated in separate but identical
metal heat sinks. The output is the difference in power needed
to maintain the heat sinks at equal temperatures as the
temperature rises.
and α is the scan rate. A computer controls the electrical power
supply that maintains the same temperature in the sample and
reference compartments throughout the analysis (Fig. 2C.3).
If no physical or chemical change occurs in the sample at
temperature T, we write the heat transferred to the sample as
qp = CpΔT, where ΔT = T − T0 and we have assumed that Cp is
independent of temperature. Because T = T0 + αt, ΔT = αt. The
chemical or physical process requires the transfer of qp + qp,ex,
where qp,ex is the excess energy transferred as heat needed to
attain the same change in temperature of the sample as the con-
trol. The quantity qp,ex is interpreted in terms of an apparent
change in the heat capacity at constant pressure of the sample,
Cp, during the temperature scan:
q p,ex q p,ex Pex
C p,ex = = = (2C.8)
∆T αt α
where Pex = qp,ex/t is the excess electrical power necessary to
equalize the temperature of the sample and reference compart-
ments. A DSC trace, also called a thermogram, consists of a
plot of Cp,ex against T (Fig. 2C.4). The enthalpy change associ-
ated with the process is
T2
∆H = ∫ T1
C p,ex dT (2C.9)
where T1 and T2 are, respectively, the temperatures at which the
process begins and ends. This relation shows that the enthalpy
change is equal to the area under the plot of Cp,ex against T.
The technique is used, for instance, to assess the stability
of proteins, nucleic acids, and membranes. The thermogram
shown in Fig. 2C.4 indicates that the protein ubiquitin under-
goes an endothermic conformational change in which a large
number of non-covalent interactions (such as hydrogen bonds)
are broken simultaneously and result in denaturation, the loss
of the protein’s three-dimensional structure. The area under
the curve represents the heat absorbed in this process and
88 2 The First Law

9 Injector
Cp,ex/(mJ K–1)

6
Reference Sample
cell cell

Heater Heater

0
30 45 60 75 90
Temperature comparison
Temperature, θ /°C
Figure 2C.5 A schematic diagram of the apparatus used for
Figure 2C.4 A thermogram for the protein ubiquitin at
isothermal titration calorimetry.
pH = 2.45. The protein retains its native structure up to about
45 °C and then undergoes an endothermic conformational
change. (Adapted from B. Chowdhry and S. LeHarne, J. Chem.
Educ. 74, 236 (1997).)
(a)

(a) Power, (b) ΔH

can be identified with the enthalpy change. The thermogram
also reveals the formation of new intermolecular interactions
in the denatured form. The increase in heat capacity accom-
panying the native → denatured transition reflects the change
from a more compact native conformation to one in which the
more exposed amino acid side chains in the denatured form
have more extensive interactions with the surrounding water
molecules.
(b) Isothermal titration calorimetry
Isothermal titration calorimetry (ITC) is also a ‘differential’
technique in which the thermal behaviour of a sample is com-
pared with that of a reference. The apparatus is shown in Fig.
2C.5. One of the thermally conducting vessels, which have
a volume of a few millilitres (10−6 m3), contains the reference
(water for instance) and a heater rated at a few milliwatts. The
second vessel contains one of the reagents, such as a solution of
a macromolecule with binding sites; it also contains a heater. At
the start of the experiment, both heaters are activated, and then
precisely determined amounts (of volume of about a microlitre,
10−9 m3) of the second reagent are added to the reaction cell.
The power required to maintain the same temperature differen-
tial with the reference cell is monitored. If the reaction is exo-
thermic, less power is needed; if it is endothermic, then more
power must be supplied.
(b)
Time
Figure 2C.6 (a) The record of the power applied as each
injection is made, and (b) the sum of successive enthalpy
changes in the course of the titration.
A typical result is shown in Fig. 2C.6, which shows the
power needed to maintain the temperature differential: from
the power and the length of time, δt, for which it is supplied,
the heat supplied, δqi, for the injection i can be calculated
from δqi = Piδt. If the volume of solution is V and the molar
concentration of unreacted reagent A is ci at the time of the
ith injection, then the change in its concentration at that
injection is δci and the heat generated (or absorbed) by the
reaction is VΔrHδci = δqi. The sum of all such quantities, given
that the sum of δci is the known initial concentration of the
reactant, can then be interpreted as the value of ΔrH for the
reaction.

Checklist of concepts
☐ 1. The standard enthalpy of transition is equal to the energy
transferred as heat at constant pressure in the transition.
☐ 2. A thermochemical equation is a chemical equation
and its associated change in enthalpy.
☐ 3. Hess’s law states that the standard enthalpy of an over-
all reaction is the sum of the standard enthalpies of
the individual reactions into which a reaction may be
divided.
 2c Thermochemistry 89

☐ 4. Standard enthalpies of formation are defined in terms ☐ 6. Computer modelling is used to estimate standard
of the reference states of elements. enthalpies of formation.
☐ 5. The standard reaction enthalpy is expressed as the dif- ☐ 7. The temperature dependence of a reaction enthalpy is
ference of the standard enthalpies of formation of prod- expressed by Kirchhoff’s law.
ucts and reactants.

Checklist of equations
Property Equation Comment Equation number

∑ ∆ H ∑
The standard reaction enthalpy ν: stoichiometric coefficients; 2C.5
∆r H < = f
<− ∆ f H <
νJ: (signed) stoichiometric numbers
Products Reactants

∆r H< = ∑ ∆
J
J f H <(J)

T2
Kirchhoff’s law ∆ r H <(T2 ) = ∆ r H <(T2 ) +
∫T1
∆rC <
p dT 2C.7a

∆ rC <
p ,m = ∑ C
J
J p,m (J)
<
2C.7c

∆ r H <(T2 ) = ∆ r H <(T1 ) + (T2 −T1 ) ∆ r C <

p If ∆ r C p< independent of temperature
2D State functions and exact differentials
Contents
2D.1 Exact and inexact differentials
Example 2D.1: Calculating work, heat, and
change in internal energy
2D.2 Changes in internal energy
(a) General considerations
(b) Changes in internal energy at constant pressure
Example 2D.2: Calculating the expansion
coefficient of a gas
Brief illustration 2D.1: The relation between heat
capacities
2D.3 The Joule–Thomson effect
(a) Observation of the Joule–Thomson effect
Brief illustration 2D.2: The Joule–Thompson effect
(b) The molecular interpretation of the
Joule–Thomson effect
Checklist of concepts
Checklist of equations
➤➤ Why do you need to know this material?
Thermodynamics gives us the power to derive relations
between a variety of properties: this Topic is a first
introduction to the manipulation of equations involving
state functions. In the process, we obtain such important
relations as that between heat capacities. An important
technological consequence is the Joule–Thomson effect
for cooling gases, which is derived here.
➤➤ What is the key idea?
The fact that internal energy and enthalpy are state
functions leads to relations between thermodynamic
properties.
➤➤ What do you need to know already?
You need to be aware that internal energy and enthalpy
are state functions (Topics 2B and 2C) and be familiar with
heat capacity. You need to be able to make use of several
simple relations involving partial derivatives (Mathematical
background 2).
A state function is a property that depends only on the current
state of a system and is independent of its history. The inter-
nal energy and enthalpy are two examples of state functions.
90
Physical quantities that do depend on the path between two
states are called path functions. Examples of path functions are
91
the work and the heating that are done when preparing a state.
91
We do not speak of a system in a particular state as possessing
91
work or heat. In each case, the energy transferred as work or
93
heat relates to the path being taken between states, not the cur-
rent state itself.
93
A part of the richness of thermodynamics is that it uses the
94 mathematical properties of state functions to draw far-reach-
ing conclusions about the relations between physical proper-
95
ties and thereby establish connections that may be completely
95
unexpected. The practical importance of this ability is that we
97
can combine measurements of different properties to obtain
98 the value of a property we require.
98
99
2D.1 Exact and inexact differentials
Consider a system undergoing the changes depicted in Fig. 2D.1.
The initial state of the system is i and in this state the internal
energy is Ui. Work is done by the system as it expands adiabati-
cally to a state f. In this state the system has an internal energy
Uf and the work done on the system as it changes along Path 1
from i to f is w. Notice our use of language: U is a property of
the state; w is a property of the path. Now consider another pro-
cess, Path 2, in which the initial and final states are the same as
those in Path 1 but in which the expansion is not adiabatic. The
internal energy of both the initial and the final states are the same
as before (because U is a state function). However, in the second
path an energy q′ enters the system as heat and the work w′ is not
the same as w. The work and the heat are path functions.
If a system is taken along a path (for example, by heating
it), U changes from Ui to Uf, and the overall change is the sum
(integral) of all the infinitesimal changes along the path:
f
∆U = ∫ dU
i
(2D.1)
The value of ΔU depends on the initial and final states of the
system but is independent of the path between them. This path-
independence of the integral is expressed by saying that dU
 2D State functions and exact differentials 91

simplest are the following: Path 1, in which there is free expan-

sion against zero external pressure; Path 2, in which there is

Internal energy, U
i Path 1
(w ≠ 0, q = 0) reversible, isothermal expansion. Calculate w, q, and ΔU for
each process.
Path 2
(w ≠ 0, q ≠ 0) Method To find a starting point for a calculation in thermo-
dynamics, it is often a good idea to go back to first principles
f
and to look for a way of expressing the quantity we are asked to
calculate in terms of other quantities that are easier to calcu-
Temperature, T late. It is argued in Topic 2B that the internal energy of a per-
Volume, V fect gas depends only on the temperature and is independent
of the volume those molecules occupy, so for any isothermal
change, ΔU = 0. We also know that in general ΔU = q + w. The
Figure 2D.1 As the volume and temperature of a system are question depends on being able to combine the two expres-
changed, the internal energy changes. An adiabatic and a non- sions. Topic 2A presents a number of expressions for the work
adiabatic path are shown as Path 1 and Path 2, respectively: done in a variety of processes, and here we need to select the
they correspond to different values of q and w but to the same appropriate ones.
value of ΔU. Answer Because ΔU = 0 for both paths and ΔU = q + w, in each
case q = −w. The work of free expansion is zero (eqn 2A.7 of
is an ‘exact differential’. In general, an exact differential is an Topic 2A, w = 0); so in Path 1, w = 0 and therefore q = 0 too. For
infinitesimal quantity that, when integrated, gives a result that Path 2, the work is given by eqn 2A.9 of Topic 2A (w = −nRT
ln(Vf/Vi)) and consequently q = nRT ln(Vf/Vi).
is independent of the path between the initial and final states.
When a system is heated, the total energy transferred as heat is Self-test 2D.1 Calculate the values of q, w, and ΔU for an irre-
the sum of all individual contributions at each point of the path: versible isothermal expansion of a perfect gas against a con-
stant nonzero external pressure.
f
q= ∫
i , path
dq (2D.2) Answer: q = pex ΔV, w = −pex ΔV, ΔU = 0

Notice the differences between this equation and eqn 2D.1.

First, we do not write Δq, because q is not a state function 2D.2 Changes in internal energy
and the energy supplied as heat cannot be expressed as qf − qi.
Secondly, we must specify the path of integration because q We begin to unfold the consequences of dU being an exact dif-
depends on the path selected (for example, an adiabatic path ferential by exploring a closed system of constant composition
has q = 0, whereas a non-adiabatic path between the same two (the only type of system considered in the rest of this Topic).
states would have q ≠ 0). This path-dependence is expressed by The internal energy U can be regarded as a function of V, T,
saying that dq is an ‘inexact differential’. In general, an inexact and p, but, because there is an equation of state (Topic 1A), stat-
differential is an infinitesimal quantity that, when integrated, ing the values of two of the variables fixes the value of the third.
gives a result that depends on the path between the initial and Therefore, it is possible to write U in terms of just two inde-
final states. Often dq is written đq to emphasize that it is inexact pendent variables: V and T, p and T, or p and V. Expressing U
and requires the specification of a path. as a function of volume and temperature fits the purpose of our
The work done on a system to change it from one state to discussion.
another depends on the path taken between the two specified
states; for example, in general the work is different if the change
takes place adiabatically and non-adiabatically. It follows that
(a) General considerations
dw is an inexact differential. It is often written đw. Because the internal energy is a function of the volume and the
temperature, when these two quantities change, the internal
Example 2D.1
energy changes by
Calculating work, heat, and change in
internal energy  ∂U   ∂U  General expression
dU =  dV +  dT for a change in U (2D.3)
Consider a perfect gas inside a cylinder fitted with a piston. Let  ∂V  T  ∂T  V with T and V
the initial state be T,Vi and the final state be T,Vf. The change
of state can be brought about in many ways, of which the two The interpretation of this equation is that, in a closed system of
constant composition, any infinitesimal change in the internal
92 2 The First Law
Internal energy, U
U
dT
Volume, V dV
Figure 2D.2 An overall change in U, which is denoted dU,
arises when both V and T are allowed to change. If second-
order infinitesimals are ignored, the overall change is the sum
of changes for each variable separately.
energy is proportional to the infinitesimal changes of volume
and temperature, the coefficients of proportionality being the
two partial derivatives (Fig. 2D.2).
In many cases partial derivatives have a straightforward
physical interpretation, and thermodynamics gets shapeless
and difficult only when that interpretation is not kept in sight.
In the present case, we have already met (∂U/∂T)V in Topic 2A,
where we saw that it is the constant-volume heat capacity, CV.
The other coefficient, (∂U/∂V)T , plays a major role in thermo-
dynamics because it is a measure of the variation of the internal
energy of a substance as its volume is changed at constant tem-
perature (Fig. 2D.3). We shall denote it πT and, because it has
the same dimensions as pressure but arises from the interac-
tions between the molecules within the sample, call it the inter-
nal pressure:
 ∂U 
πT =  Definition
 ∂V  T
Internal energy, U
πT
U
dV
Volume, V
Figure 2D.3 The internal pressure, πT, is the slope of U with
respect to V with the temperature T held constant.
Repulsions
dominant, πT < 0
Internal energy, U
Perfect gas
U+ ( ∂U
∂V )
T
+ ( ∂T )
dV ∂U dT
V
Attractions
dominant, πT > 0
Temperature, T
Volume, V
Figure 2D.4 For a perfect gas, the internal energy is
independent of the volume (at constant temperature). If
attractions are dominant in a real gas, the internal energy
increases with volume because the molecules become farther
apart on average. If repulsions are dominant, the internal
energy decreases as the gas expands.
In terms of the notation CV and πT , eqn 2D.3 can now be written
dU = π T dV + CV dT (2D.5)
When there are no interactions between the molecules, the
internal energy is independent of their separation and hence
independent of the volume of the sample. Therefore, for a per-
fect gas we can write πT = 0. If the gas is described by the van der
Waals equation with a, the parameter corresponding to attrac-
tive interactions, dominant, then an increase in volume increases
the average separation of the molecules and therefore raises the
internal energy. In this case, we expect πT > 0 (Fig. 2D.4).
The statement πT = 0 (that is, the internal energy is independ-
ent of the volume occupied by the sample) can be taken to be
the definition of a perfect gas, for in Topic 3D we see that it
implies the equation of state pV ∝ T.
James Joule thought that he could measure πT by observing
(2D.4)
Internal pressure
the change in temperature of a gas when it is allowed to expand
into a vacuum. He used two metal vessels immersed in a water
bath (Fig. 2D.5). One was filled with air at about 22 atm and
the other was evacuated. He then tried to measure the change
High pressure Vacuum
gas
Temperature, T
Figure 2D.5 A schematic diagram of the apparatus used by
Joule in an attempt to measure the change in internal energy
when a gas expands isothermally. The heat absorbed by the
gas is proportional to the change in temperature of the bath.
 2D State functions and exact differentials 93

in temperature of the water of the bath when a stopcock was Table 2D.1* Expansion coefficients (α) and
opened and the air expanded into a vacuum. He observed no isothermal compressibilities (κT) at 298 K
change in temperature.
α/(10−4 K−1) κT/(10−6 bar−1)
The thermodynamic implications of the experiment are as
Benzene 12.4 90.9
follows. No work was done in the expansion into a vacuum,
so w = 0. No energy entered or left the system (the gas) as heat Diamond 0.030 0.185
because the temperature of the bath did not change, so q = 0. Lead 0.861 2.18
Consequently, within the accuracy of the experiment, ΔU = 0. Water 2.1 49.0
Joule concluded that U does not change when a gas expands * More values are given in the Resource section.
isothermally and therefore that πT = 0. His experiment, how-
ever, was crude. In particular, the heat capacity of the apparatus
1  ∂V 
was so large that the temperature change that gases do in fact κT = − Definition Isothermal compressibility (2D.7)
V  ∂p  T
cause was too small to measure. Nevertheless, from his experi-
ment Joule had extracted an essential limiting property of a gas,
a property of a perfect gas, without detecting the small devia- The isothermal compressibility is a measure of the fractional
tions characteristic of real gases. change in volume when the pressure is increased by a small
amount; the negative sign in the definition ensures that the
compressibility is a positive quantity, because an increase of
(b) Changes in internal energy at pressure, implying a positive dp, brings about a reduction of
volume, a negative dV.
constant pressure
Partial derivatives have many useful properties and some that Example 2D.2 Calculating the expansion coefficient of
we shall draw on frequently are reviewed in Mathematical back- a gas
ground 2. Skilful use of them can often turn some unfamiliar
quantity into a quantity that can be recognized, interpreted, or Derive an expression for the expansion coefficient of a perfect
measured. gas.
As an example, suppose we want to find out how the internal Method The expansion coefficient is defined in eqn 2D.6. To
energy varies with temperature when the pressure rather than use this expression, substitute the expression for V in terms of
the volume of the system is kept constant. If we divide both T obtained from the equation of state for the gas. As implied
sides of eqn 2D.5 by dT and impose the condition of constant by the subscript in eqn 2D.6, the pressure, p, is treated as a
pressure on the resulting differentials, so that dU/dT on the left constant.
becomes (∂U/∂T)p, we obtain
Answer Because pV = nRT, we can write
 ∂U   ∂V 
 ∂T  = π T  ∂T  + CV α=
1  ∂(nRT / p)  1 nR dT nR 1
p p V  ∂T  = V × p dT = pV = T
p

It is usually sensible in thermodynamics to inspect the output

of a manipulation like this to see if it contains any recogniz-
able physical quantity. The partial derivative on the right in
this expression is the slope of the plot of volume against tem-
perature (at constant pressure). This property is normally tabu-
lated as the expansion coefficient, α, of a substance, which is
defined as
The higher the temperature, the less responsive is the volume
of a perfect gas to a change in temperature.
Self-test 2D.2 Derive an expression for the isothermal com-
pressibility of a perfect gas.
Answer: κT =1/p

1  ∂V  When we introduce the definition of α into the equation for

α= (2D.6)
V  ∂T  p
Definition Expansion coefficient
(∂U/∂T)p, we obtain

and physically is the fractional change in volume that accom-  ∂U 

panies a rise in temperature. A large value of α means that the
volume of the sample responds strongly to changes in tem-
perature. Table 2D.1 lists some experimental values of α. For
future reference, it also lists the isothermal compressibility, κT
(kappa), which is defined as
 ∂T  = απ T V + CV (2D.8)
p
This equation is entirely general (provided the system is closed
and its composition is constant). It expresses the dependence
of the internal energy on the temperature at constant pressure
94 2 The First Law

in terms of CV, which can be measured in one experiment, in

terms of α, which can be measured in another, and in terms of (2.1 × 10−4 K −1 )2 × (298 K ) × (1.81 × 10−5 m3 mol −1 )
C p, m − CV , m =
the quantity πT. For a perfect gas, πT = 0, so then 4.90 × 10−10 Pa −1
= 0.485 Pa m3 mol −1 = 0.485 Jmol −1
 ∂U 
 ∂T  = CV (2D.9)
For water, Cp,m = 75.3 J K−1 mol−1, so CV,m = 74.8 J K−1 mol−1. In
p
some cases, the two heat capacities differ by as much as 30 per
That is, although the constant-volume heat capacity of a perfect cent.
gas is defined as the slope of a plot of internal energy against Self-test 2D.3 Evaluate the difference in molar heat capacities
temperature at constant volume, for a perfect gas CV is also the for benzene; use data from the Resource section.
slope at constant pressure.
Answer: 45 J K−1 mol−1
Equation 2D.9 provides an easy way to derive the relation
between Cp and CV for a perfect gas. Thus, we can use it to
express both heat capacities in terms of derivatives at constant
pressure:

Definition
of C p eqn 2D.9 Justification 2D.1 The relation between heat capacities

      
 ∂H   ∂U  A useful rule when doing a problem in thermodynamics is to
C p − CV =  −
 ∂T  p  ∂T  p go back to first principles. In the present problem we do this
twice, first by expressing Cp and CV in terms of their defini-
Then we introduce H =U + pV = U + nRT into the first term, tions and then by inserting the definition H = U + pV:
which results in
 ∂H 
C p − CV =  −C
 ∂(U + nRT )   ∂U   ∂T  p V
C p − CV =   −  ∂T  = nR (2D.10)
 ∂T  ∂U   ∂( pV ) 
p p
= + −C
 ∂T  p  ∂T  p V
We show in the following Justification that in general
Equation 2D.8, (∂U/∂T)p = απTV + CV, lets us write the differ-
α 2TV ence of the first and third terms as απTV. We can simplify the
C p − CV = (2D.11)
κT remaining term by noting that, because p is constant,

Equation 2D.11 applies to any substance (that is, it is ‘univer-  ∂( pV )   ∂V 

 ∂T  = p  ∂T  = α pV
sally true’). It reduces to eqn 2D.10 for a perfect gas when we p p
set α  = 1/T and κT = 1/p. Because expansion coefficients α of
liquids and solids are small, it is tempting to deduce from eqn Collecting the two contributions gives
2D.11 that for them Cp ≈ CV. But this is not always so, because
the compressibility κT might also be small, so α2/κT might be C p − CV = α ( p + π T )V
large. That is, although only a little work need be done to push
back the atmosphere, a great deal of work may have to be done The first term on the right, αpV, is a measure of the work
to pull atoms apart from one another as the solid expands. needed to push back the atmosphere; the second term on the
right, απ TV, is the work required to separate the molecules
composing the system.
Brief illustration 2D.1 The relation between heat At this point we can go further by using the (Second Law)
capacities result proved in Topic 3D that

The expansion coefficient and isothermal compressibility

 ∂p 
of water at 25 °C are given in Table 2D.1 as 2.1 × 10 −4 K−1 and πT =T  −p
 ∂T  V
4.96 × 10−5 atm−1 (4.90 × 10−10 Pa−1), respectively. The molar vol-
ume of water at that temperature, Vm = M/ρ (where ρ is the
When this expression is inserted in the last equation we obtain
mass density) is 18.1 cm3 mol−1 (1.81 × 10−5 m3 mol−1). Therefore,
from eqn 2D.11, the difference in molar heat capacities (which
is given by Vm in place of V) is  ∂p 
C p − CV = αTV 
 ∂T  V
 2D State functions and exact differentials 95

We now transform the remaining partial derivative. With V  ∂H   ∂H 

regarded as a function of p and T, when these two quantities dH =   dp +  dT
 ∂ p T  ∂T  p
change the resulting change in V is

 ∂V   ∂V  The second partial derivative is Cp; our task here is to express

dV =  dT +  dp (∂H/∂p)T in terms of recognizable quantities. If the enthalpy is
 ∂T  p  ∂p  T
constant, dH = 0 and this expression then requires that
For the volume to be constant, dV = 0 implies that
 ∂H 
 ∂p  dp = −C pdT at constant H
 ∂V   ∂V  T
 ∂T  dT = −  ∂p  dp at constant volume
p T Division of both sides by dp then gives
On division by dT, this relation becomes
 ∂H   ∂T 
 ∂p  = −C p  ∂p  = −C p μ
 ∂V   ∂V   ∂p  T H
 ∂T  = −  ∂p   ∂T 
p T V Equation 2D.13 now follows directly.
and therefore

 ∂p  ( ∂V / ∂T ) p α (a) Observation of the Joule–Thomson effect

 ∂T  = − (∂V / ∂p) = κ
V T T
The analysis of the Joule–Thomson coefficient is central to
Insertion of this relation into the expression above for Cp − CV the technological problems associated with the liquefaction
produces eqn 2D.11. of gases. We need to be able to interpret it physically and to
measure it. As shown in the following Justification, the cunning
required to impose the constraint of constant enthalpy, so that
2D.3 The Joule–Thomson effect the process is isenthalpic, was supplied by Joule and William
Thomson (later Lord Kelvin). They let a gas expand through
We can carry out a similar set of operations on the enthalpy, a porous barrier from one constant pressure to another and
H = U + pV. The quantities U, p, and V are all state functions; monitored the difference of temperature that arose from the
therefore H is also a state function and dH is an exact differ- expansion (Fig. 2D.6). The whole apparatus was insulated so
ential. It turns out that H is a useful thermodynamic function that the process was adiabatic. They observed a lower tempera-
when the pressure is under our control: we saw a sign of that ture on the low pressure side, the difference in temperature
in the relation ΔH = qp (this is eqn 2B.2b of Topic 2B). We shall being proportional to the pressure difference they maintained.
therefore regard H as a function of p and T, and adapt the argu-
ment in Section 2D.2 for the variation of U to find an expression
for the variation of H with temperature at constant volume. As
explained in the following Justification, we find that for a closed
system of constant composition,
Gas at
Thermocouples low
d H = − μC p d p + C p d T (2D.12)
pressure
where the Joule–Thomson coefficient, μ (mu), is defined as
Porous
barrier
 ∂T 
μ = (2D.13)
 ∂p  H
Definition Joule–Thomson coefficient

This relation will prove useful for relating the heat capacities at
Gas at
constant pressure and volume and for a discussion of the lique- high pressure
faction of gases.
Figure 2D.6 The apparatus used for measuring the Joule–
Justification 2D.2
The variation of enthalpy with Thomson effect. The gas expands through the porous
barrier, which acts as a throttle, and the whole apparatus is
pressure and temperature
thermally insulated. As explained in the text, this arrangement
Because H is a function of p and T we can write, when these corresponds to an isenthalpic expansion (expansion at
two quantities change by an infinitesimal amount, the constant enthalpy). Whether the expansion results in a heating
enthalpy changes by or a cooling of the gas depends on the conditions.
96 2 The First Law
This cooling by isenthalpic expansion is now called the Joule–
Thomson effect.
Justification 2D.3 The Joule–Thomson effect
Here we show that the experimental arrangement results in
expansion at constant enthalpy. Because all changes to the gas
occur adiabatically, q = 0 implies that ΔU = w. Next, consider
the work done as the gas passes through the barrier. We focus
on the passage of a fixed amount of gas from the high pressure
side, where the pressure is pi, the temperature Ti, and the gas
occupies a volume Vi (Fig. 2D.7).
Throttle
Upstream Downstream
pi, Vi, Ti
pressure p pf pressure
i
pi pf
pf, Vf, Tf
pf
pi
Figure 2D.7 The thermodynamic basis of Joule–Thomson
expansion. The pistons represent the upstream and
downstream gases, which maintain constant pressures
either side of the throttle. The transition from the top
diagram to the bottom diagram, which represents the
passage of a given amount of gas through the throttle,
occurs without change of enthalpy.
The gas emerges on the low pressure side, where the same
amount of gas has a pressure pf, a temperature Tf, and occupies
a volume Vf. The gas on the left is compressed isothermally by
the upstream gas acting as a piston. The relevant pressure is pi
and the volume changes from Vi to 0; therefore, the work done
on the gas is
w1 = − pi (0 − Vi ) = piVi
The gas expands isothermally on the right of the barrier (but
possibly at a different constant temperature) against the pres-
sure pf provided by the downstream gas acting as a piston to be
driven out. The volume changes from 0 to Vf, so the work done
on the gas in this stage is
w2 = − pf (Vf − 0) = − pf Vf
The total work done on the gas is the sum of these two quanti-
ties, or
w1 + w2 = piVi − pf Vf
It follows that the change of internal energy of the gas as it
moves adiabatically from one side of the barrier to the other is
U f −U i = w = piVi − pf Vf
Reorganization of this expression gives
U f + pf Vf = U i + piVi or H f = H i
Therefore, the expansion occurs without change of enthalpy.
The property measured in the experiment is the ratio of the
temperature change to the change of pressure, ΔT/Δp. Adding the
constraint of constant enthalpy and taking the limit of small Δp
implies that the thermodynamic quantity measured is (∂T/∂p)H,
which is the Joule–Thomson coefficient, μ. In other words, the
physical interpretation of μ is that it is the ratio of the change in
temperature to the change in pressure when a gas expands under
conditions that ensure there is no change in enthalpy.
The modern method of measuring μ is indirect, and involves
measuring the isothermal Joule–Thomson coefficient, the
quantity
 ∂H  Isothermal
μT =  Definition Joule–Thomson (2D.14)
 ∂p  T coefficient
which is the slope of a plot of enthalpy against pressure at con-
stant temperature (Fig. 2D.8). Comparing eqns 2D.13 and
2D.14, we see (from the last line of Justification 2D.2) that the
two coefficients are related by:
μT = −C p μ
(2D.15)
To measure μT, the gas is pumped continuously at a steady pres-
sure through a heat exchanger, which brings it to the required
temperature, and then through a porous plug inside a thermally
insulated container. The steep pressure drop is measured and
the cooling effect is exactly offset by an electric heater placed
immediately after the plug (Fig. 2D.9). The energy provided
µT = ( ∂H
∂p )
T
Enthalpy, H
Temperature, T
Pressure, p
Figure 2D.8 The isothermal Joule–Thomson coefficient is the
slope of the enthalpy with respect to changing pressure, the
temperature being held constant.
 2D State functions and exact differentials 97

Porous
Heater
plug ∆T ≈ μ∆p = +(0.25 K bar −1 ) × (−10 bar) = −2.5 K

At the same initial temperature and pressure, the molar iso-

thermal Joule coefficient is
Gas flow
μT , m = −C p, m μ = −(29.1JK −1 mol −1 ) × (+0.25 K bar −1 )
= −7.3 J bar −1 mol −1

Note that μ is an intensive property but μ T is extensive (but

Thermocouples
Figure 2D.9 A schematic diagram of the apparatus used for
measuring the isothermal Joule–Thomson coefficient. The
electrical heating required to offset the cooling arising from
expansion is interpreted as ΔH and used to calculate (∂H/∂p)T,
which is then converted to µ as explained in the text.
μT,m, like all molar quantities, is intensive).
Self-test 2D.4 Evaluate the change in temperature when the
pressure of carbon dioxide changes isenthalpically by −10 bar
at 300 K and evaluate its molar isothermal Joule coefficient.
Answer: −11 K, 41.2 J bar−1 mol−1

Heating
Table 2D.2* Inversion temperatures (TI), normal freezing (Tf )
and boiling (Tb) points, and Joule–Thomson coefficients (μ) at
µ>0

Temperature, T
1 atm and 298 K

TI/K Tf/K Tb/K μ/(K bar−1) Cooling

Ar 723 83.8 87.3

CO2 1500 194.7 +1.10
He 40 4.2 −0.060
N2 621 63.3 77.4 +0.25
* More values are given in the Resource section.
by the heater is monitored. Because ΔH = qp, the energy trans-
ferred as heat can be identified with the value of ΔH. The pres-
sure change Δp is known, so we can find μT from the limiting
value of ΔH/Δp as Δp → 0 and then convert it to μ. Table 2D.2
lists some values obtained in this way.
Real gases have nonzero Joule–Thomson coefficients.
Depending on the identity of the gas, the pressure, the rela-
tive magnitudes of the attractive and repulsive intermolecular
forces, and the temperature, the sign of the coefficient may be
either positive or negative (Fig. 2D.10). A positive sign implies
that dT is negative when dp is negative, in which case the gas
cools on expansion. Gases that show a heating effect (μ < 0) at
one temperature show a cooling effect (μ > 0) when the tem-
perature is below their upper inversion temperature, T1 (Table
2D.2, Fig. 2D.11). As indicated in Fig. 2D.11, a gas typically has
two inversion temperatures.
Brief illustration 2D.2
The Joule–Thomson effect
The Joule–Thomson coefficient for nitrogen at 298 K and 1 atm
(Table 2D.2) is +0.25 K bar−1. It follows that the change in tem-
perature the gas undergoes when its pressure changes by −10
bar under isenthalpic conditions is
µ<0
Pressure, p
Figure 2D.10 The sign of the Joule–Thomson coefficient, μ,
depends on the conditions. Inside the boundary, the blue
area, it is positive and outside it is negative. The temperature
corresponding to the boundary at a given pressure is the
‘inversion temperature’ of the gas at that pressure. For a given
pressure, the temperature must be below a certain value if
cooling is required but, if it becomes too low, the boundary
is crossed again and heating occurs. Reduction of pressure
under adiabatic conditions moves the system along one of
the isenthalps, or curves of constant enthalpy. The inversion
temperature curve runs through the points of the isenthalps
where their slope changes from negative to positive.
The ‘Linde refrigerator’ makes use of Joule–Thomson expan-
sion to liquefy gases (Fig. 2D.12). The gas at high pressure is
allowed to expand through a throttle; it cools and is circulated
past the incoming gas. That gas is cooled, and its subsequent
expansion cools it still further. There comes a stage when the
circulating gas becomes so cold that it condenses to a liquid.
For a perfect gas, μ = 0; hence, the temperature of a per-
fect gas is unchanged by Joule–Thomson expansion. (Simple
adiabatic expansion does cool a perfect gas, because the gas
does work, Topic 2E.) This characteristic points clearly to the
involvement of intermolecular forces in determining the size of
the effect. However, the Joule–Thomson coefficient of a real gas
98 2 The First Law

600
Upper (b)The molecular interpretation of the
inversion Heating
temperature
Joule–Thomson effect
Temperature, T/K

400 The kinetic model of gases (Topic 1B) and the equipartition
Cooling
Nitrogen theorem (Foundations B) jointly imply that the mean kinetic
µ>0 energy of molecules in a gas is proportional to the temperature.
It follows that reducing the average speed of the molecules is
200
Lower µ<0 equivalent to cooling the gas. If the speed of the molecules can
Hydrogen inversion be reduced to the point that neighbours can capture each other
temperature by their intermolecular attractions, then the cooled gas will
Helium
0
0 200 400 condense to a liquid.
Pressure, p To slow the gas molecules, we make use of an effect simi-
lar to that seen when a ball is thrown into the air: as it rises
Figure 2D.11 The inversion temperatures for three real gases,
it slows in response to the gravitational attraction of the Earth
nitrogen, hydrogen, and helium.
and its kinetic energy is converted into potential energy. We
saw in Topic 1C that molecules in a real gas attract each other
(the attraction is not gravitational, but the effect is the same). It
Cold gas follows that, if we can cause the molecules to move apart from
each other, like a ball rising from a planet, then they should
Heat
exchanger slow. It is very easy to move molecules apart from each other:
we simply allow the gas to expand, which increases the average
separation of the molecules. To cool a gas, therefore, we allow
it to expand without allowing any energy to enter from outside
Throttle as heat. As the gas expands, the molecules move apart to fill
the available volume, struggling as they do so against the attrac-
Liquid
tion of their neighbours. Because some kinetic energy must be
Compressor converted into potential energy to reach greater separations,
the molecules travel more slowly as their separation increases.
Figure 2D.12 The principle of the Linde refrigerator is shown This sequence of molecular events explains the Joule–Thomson
in this diagram. The gas is recirculated, and so long as it is effect: the cooling of a real gas by adiabatic expansion. The cool-
beneath its inversion temperature it cools on expansion ing effect, which corresponds to μ > 0, is observed under condi-
through the throttle. The cooled gas cools the high-pressure tions when attractive interactions are dominant (Z < 1, where
gas, which cools still further as it expands. Eventually liquefied Z is the compression factor defined in eqn 1C.1, Z = Vm /Vm°),
gas drips from the throttle. because the molecules have to climb apart against the attrac-
tive force in order for them to travel more slowly. For molecules
does not necessarily approach zero as the pressure is reduced under conditions when repulsions are dominant (Z > 1), the
even though the equation of state of the gas approaches that of Joule–Thomson effect results in the gas becoming warmer, or
a perfect gas. The coefficient behaves like the properties dis- μ < 0.
cussed in Topic 1C in the sense that it depends on derivatives
and not on p, V, and T themselves.

Checklist of concepts
☐ 1. The quantity dU is an exact differential; dw and dq
are not.
☐ 2. The change in internal energy may be expressed in
terms of changes in temperature and pressure.
☐ 3. The internal pressure is the variation of internal energy
with volume at constant temperature.
☐ 4. Joule’s experiment showed that the internal pressure of
a perfect gas is zero.
☐ 5. The change in internal energy with pressure and tem-
perature is expressed in terms of the internal pressure
and the heat capacity and leads to a general expression
for the relation between heat capacities.
☐ 6. The Joule–Thomson effect is the change in temperature
of a gas when it undergoes isenthalpic expansion.
 2D State functions and exact differentials 99

Checklist of equations
Property Equation Comment Equation number

Change in U(V,T) dU = (∂U/∂V)T dV + (∂U/∂T)V dT Constant composition 2D.3

Internal pressure πT = (∂U/∂V)T Definition; for a perfect gas, πT = 0 2D.4

Change in U(V,T) dU = πTdV + CVdT Constant composition 2D.5

Expansion coefficient α = (1/V)(∂V/∂T)p Definition 2D.6

Isothermal compressibility κT = − (1/V)(∂V/∂p)T Definition 2D.7

Relation between heat capacities Cp − CV = nR Perfect gas 2D.10

Cp − CV = α2TV/κT 2D.11

Change in H(p,T) dH = –μCpdp + CpdT Constant composition 2D.12

Joule–Thomson coefficient μ = (∂T/∂p)H For a perfect gas, μ = 0 2D.13

Isothermal Joule–Thomson coefficient μT = (∂H/∂p)T For a perfect gas, μT = 0 2D.14

Relation between coefficients μT = −Cpμ 2D.15

2E Adiabatic changes

Contents Ti Ti,Vi
1 U constant
Ti,Vf
2
2E.1 The change in temperature 100

ΔU = CV ΔT
Temperature, T
Brief illustration 2E.1: The change in temperature 101
2E.2 The change in pressure 101
Brief illustration 2E.2: Adiabatic expansion 102
Checklist of concepts 102
Tf
Checklist of equations 102 Tf,Vf

Vi Vf
Volume, V

➤➤ Why do you need to know this material?
Adiabatic processes complement isothermal processes,
and are used in the discussion of the Second Law of
thermodynamics.
➤➤ What is the key idea?
The temperature of a perfect gas falls when it does work in
an adiabatic expansion.
Figure 2E.1 To achieve a change of state from one
temperature and volume to another temperature and volume,
we may consider the overall change as composed of two steps.
In the first step, the system expands at constant temperature;
there is no change in internal energy if the system consists of a
perfect gas. In the second step, the temperature of the system
is reduced at constant volume. The overall change in internal
energy is the sum of the changes for the two steps.

➤➤ What do you need to know already? energy of a perfect gas is independent of the volume the mol-
This Topic makes use of the discussion of the properties ecules occupy (Topic 2A), the overall change in internal energy
of gases (Topic 1A), particularly the perfect gas law. It also arises solely from the second step, the change in temperature at
uses the definitions of heat capacity at constant volume constant volume. Provided the heat capacity is independent of
(Topic 1B) and constant pressure (Topic 2B), and the temperature, this change is
relation between them (Topic 2D).
∆U = (Tf − Ti )CV = CV ∆T
Because the expansion is adiabatic, we know that q = 0; then
The temperature falls when a gas expands adiabatically (in a because ΔU = q + w, it follows that ΔU = wad. The subscript ‘ad’
thermally insulated container). Work is done, but as no heat denotes an adiabatic process. Therefore, by equating the two
enters the system, the internal energy falls, and therefore the expressions for ΔU, we obtain
temperature of the working gas also falls. In molecular terms,
wad = CV ∆T Perfect gas Work of adiabatic change (2E.1)
the kinetic energy of the molecules falls as work is done, so their
average speed decreases, and hence the temperature falls too. That is, the work done during an adiabatic expansion of a per-
fect gas is proportional to the temperature difference between
the initial and final states. That is exactly what we expect on
molecular grounds, because the mean kinetic energy is propor-
2E.1 The change in temperature tional to T, so a change in internal energy arising from tem-
perature alone is also expected to be proportional to ΔT.
To calculate the change in temperature that results from a In the following Justification we show that, based on this
process we focus first on the change in internal energy. The result, the initial and final temperatures of a perfect gas that
change in internal energy of a perfect gas when the tempera- undergoes reversible adiabatic expansion (reversible expansion
ture is changed from Ti to Tf and the volume is changed from in a thermally insulated container) can be calculated from
Vi to Vf can be expressed as the sum of two steps (Fig. 2E.1). In Adiabatic,
1/c Final
the first step, only the volume changes and the temperature is V  reversible, tempera­ (2E.2a)
Tf = Ti  i  c = CV , m /R perfect
held constant at its initial value. However, because the internal  Vf  gas
ture
 2E Adiabatic changes 101

By raising each side of this expression to the power c, an equiva­ (We are taking CV to be independent of temperature.) Then,
lent expression is because ∫dx/x = ln x + constant, we obtain
Adiabatic,
reversible, Final Tf V
ViTi = Vf T
c c
c = CV , m /R tempera­ (2E.2b) CV ln = −nR ln f
f perfect Ti Vi
gas ture

Because ln(x/y) = –ln(y/x), this expression rearranges to

This result is often summarized in the form VTc = constant.
CV Tf V
ln = ln i
Brief illustration 2E.1 nR Ti Vf
The change in temperature
Consider the adiabatic, reversible expansion of 0.020 mol Ar, With c = CV/nR we obtain (because ln xa = a ln x)
initially at 25 °C, from 0.50 dm3 to 1.00 dm3. The molar heat
c
capacity of argon at constant volume is 12.47 J K−1 mol−1, so T  V
ln  f  = ln i
c = 1.501. Therefore, from eqn 2B.2a,  Ti  Vf

1/1.501
 0.50 dm3  which implies that (Tf /Ti)c = (Vi /Vf ) and, upon rearrangement,
Tf = (298 K )  3
= 188 K eqn 2E.2.
 1.00 dm 

It follows that ΔT = −110 K, and therefore, from eqn 2E.1, that

w = {(0.020 mol) × (12.48 JK −1 mol −1 )} × (−110 K ) = −27 J 2E.2 The change in pressure
Note that temperature change is independent of the amount of We show in the following Justification that the pressure of a per-
gas but the work is not.
fect gas that undergoes reversible adiabatic expansion from a
Self-test 2E.1 Calculate the final temperature, the work done, volume Vi to a volume Vf is related to its initial pressure by
and the change of internal energy when ammonia is used in a
Reversible adiabatic
reversible adiabatic expansion from 0.50 dm3 to 2.00 dm3, the pf Vfγ = piViγ Perfect gas
expansion (2E.3)
other initial conditions being the same.
Answer: 194 K, −56 J, −56 J where γ  = Cp,m/CV,m. This result is commonly summarized in
the form pVγ = constant.

Justification 2E.1 Changes in temperature

Justification 2E.2 The relation between pressure
Consider a stage in a reversible adiabatic expansion when
and volume
the pressure inside and out is p. The work done when the
gas expands by dV is dw = −pdV; however, for a perfect gas, The initial and final states of a perfect gas satisfy the perfect
dU = CV dT. Therefore, because for an adiabatic change (dq = 0) gas law regardless of how the change of state takes place, so we
dU = dw + dq = dw, we can equate these two expressions for dU can use pV = nRT to write
and write
piVi Ti
CV dT = − pdV =
pf Vf Tf

We are dealing with a perfect gas, so we can replace p by However, from eqn 2E.2 we know that T i /T f = (Vf /V i)1/c .
nRT/V and obtain Therefore,
CV dT nRdV 1/c 1/c +1
=− piVi  Vf  p V 
T V = , so i  i  =1
pf Vf  Vi  pf  Vf 
To integrate this expression we note that T is equal to Ti when
V is equal to Vi, and is equal to Tf when V is equal to Vf at the We now use the result from Topic 2B that C p,m − CV,m = R to
end of the expansion. Therefore, note that
Tf
dT Vf
dV 1 1 + c R + CV , m C p, m
CV ∫
Ti T
= −nR ∫
Vi V c
+1 =
c
=
CV , m
=
CV , m
=γ
102 2 The First Law

It follows that an adiabat falls more steeply (p ∝ 1/Vγ ) than the correspond-
γ ing isotherm (p ∝ 1/V). The physical reason for the difference is
pi  Vi 
=1 that, in an isothermal expansion, energy flows into the system
pf  Vf 
as heat and maintains the temperature; as a result, the pressure
does not fall as much as in an adiabatic expansion.
which rearranges to eqn 2E.3.

For a monatomic perfect gas, CV ,m = 23 R (Topic 2A) and Brief illustration 2E.2 Adiabatic expansion
C p,m = 25 R (from Cp,m − CV,m = R), so γ = 53 . For a gas of non­linear
polyatomic molecules (which can rotate as well as translate; When a sample of argon (for which γ = 53 ) at 100 kPa expands
vibrations make little contribution at normal tempera­tures), reversibly and adiabatically to twice its initial volume the final
CV,m = 3R and Cp,m = 4R, so γ = 43 . The curves of pressure versus pressure will be
volume for adiabatic change are known as adiabats, and one γ 5/3
for a reversible path is illustrated in Fig. 2E.2. Because γ  > 1, V   1
pf =  i  pi =   × (100 kPa ) = 32 kPa
 Vf   2

For an isothermal doubling of volume, the final pressure

Isotherm, p ∝ 1/V would be 50 kPa.
Adiabat, p ∝ 1/V γ Self-test 2E.2 What is the final pressure when a sample of car-
Pressure, p

bon dioxide at 100 kPa expands reversibly and adiabatically to

five times its initial volume?
Answer: 13 kPa
Pressure, p

T
e,
Volume, V tur
ra
Volume, pe
V m
Te

Figure 2E.2 An adiabat depicts the variation of pressure

with volume when a gas expands adiabatically. Note that the
pressure declines more steeply for an adiabat than it does for
an isotherm because the temperature decreases in the former.

Checklist of concepts
☐ 1. The temperature of a gas falls when it undergoes adia­ ☐ 2. An adiabat is a curve showing how pressure varies with
batic expansion (and does work). volume in an adiabatic process.

Checklist of equations
Property Equation Comment Equation number

Work of adiabatic expansion wad = CVΔT Perfect gas 2E.1

Final temperature Tf = Ti(Vi/Vf)1/c Perfect gas, reversible expansion 2E.2a

c = CV,m/R

ViTic = Vf Tfc 2E.2b

Adiabats pf Vfγ = piViγ , 2E.3

γ = C p, m /CV , m
 Exercises and problems 103

CHAPTER 2 The First Law

Assume all gases are perfect unless stated otherwise. Unless otherwise stated, thermochemical data are for 298.15 K.

TOPIC 2A Internal energy

Discussion questions
2A.1 Describe and distinguish the various uses of the words ‘system’ and ‘state’ 2A.3 Identify varieties of additional work.
in physical chemistry.
2A.2 Describe the distinction between heat and work in thermodynamic and
molecular terms, the latter in terms of populations and energy levels.

Exercises
2A.1(a) Use the equipartition theorem to estimate the molar internal energy
relative to U(0) of (i) I2, (ii) CH4, (iii) C6H6 in the gas phase at 25 °C.
2A.1(b) Use the equipartition theorem to estimate the molar internal energy
relative to U(0) of (i) O3, (ii) C2H6, (iii) SO2 in the gas phase at 25 °C.
2A.2(a) Which of (i) pressure, (ii) temperature, (iii) work, (iv) enthalpy are
state functions?
2A.2(b) Which of (i) volume, (ii) heat, (iii) internal energy, (iv) density are
state functions?
2A.3(a) A chemical reaction takes place in a container of cross-sectional area
50 cm2. As a result of the reaction, a piston is pushed out through 15 cm
against an external pressure of 1.0 atm. Calculate the work done by the
system.
2A.3(b) A chemical reaction takes place in a container of cross-sectional area
75.0 cm2. As a result of the reaction, a piston is pushed out through 25.0 cm
against an external pressure of 150 kPa. Calculate the work done by the
system.
2A.4(a) A sample consisting of 1.00 mol Ar is expanded isothermally at 20 °C
from 10.0 dm3 to 30.0 dm3 (i) reversibly, (ii) against a constant external
pressure equal to the final pressure of the gas, and (iii) freely (against zero
external pressure). For the three processes calculate q, w, and ΔU.
2A.4(b) A sample consisting of 2.00 mol He is expanded isothermally at 0 °C
from 5.0 dm3 to 20.0 dm3 (i) reversibly, (ii) against a constant external pressure
equal to the final pressure of the gas, and (iii) freely (against zero external
pressure). For the three processes calculate q, w, and ΔU.
2A.5(a) A sample consisting of 1.00 mol of perfect gas atoms, for which
CV ,m = 23 R , initially at p1 = 1.00 atm and T1 = 300 K, is heated reversibly to
400 K at constant volume. Calculate the final pressure, ΔU, q, and w.
2A.5(b) A sample consisting of 2.00 mol of perfect gas molecules, for which
CV ,m = 25 R , initially at p1 = 111 kPa and T1 = 277 K, is heated reversibly to 356 K
at constant volume. Calculate the final pressure, ΔU, q, and w.
2A.6(a) A sample of 4.50 g of methane occupies 12.7 dm3 at 310 K. (i) Calculate
the work done when the gas expands isothermally against a constant external
pressure of 200 Torr until its volume has increased by 3.3 dm3. (ii) Calculate
the work that would be done if the same expansion occurred reversibly.
2A.6(b) A sample of argon of mass 6.56 g occupies 18.5 dm3 at 305 K.
(i) Calculate the work done when the gas expands isothermally against a
constant external pressure of 7.7 kPa until its volume has increased by 2.5 dm3.
(ii) Calculate the work that would be done if the same expansion occurred
reversibly.

Problems
2A.1 Calculate the work done during the isothermal reversible expansion of a for 1.0 mol Ar at 273 K (for data, see Table 1C.1) and (b) the same amount of a
van der Waals gas (Topic 1C). Plot on the same graph the indicator diagrams perfect gas. Let the expansion be from 500 cm3 to 1000 cm3 in each case.
(graphs of pressure against volume) for the isothermal reversible expansion of
2A.4 Express the work of isothermal reversible expansion of a van der Waals
(a) a perfect gas, (b) a van der Waals gas in which a = 0 and b = 5.11 × 10−2 dm3
gas in reduced variables (Topic 1C) and find a definition of reduced work that
mol−1, and (c) a = 4.2 dm6 atm mol−2 and b = 0. The values selected exaggerate
makes the overall expression independent of the identity of the gas. Calculate
the imperfections but give rise to significant effects on the indicator diagrams.
the work of isothermal reversible expansion along the critical isotherm from
Take Vi = 1.0 dm3, n = 1.0 mol, and T = 298 K.
Vc to xVc.
2A.2 A sample consisting of 1.0 mol CaCO3(s) was heated to 800 °C, when
2A.5 Suppose that a DNA molecule resists being extended from an
it decomposed. The heating was carried out in a container fitted with a
equilibrium, more compact conformation with a restoring force F = −kf x,
piston that was initially resting on the solid. Calculate the work done during
where x is the difference in the end-to-end distance of the chain from an
complete decomposition at 1.0 atm. What work would be done if instead of
equilibrium value and kf is the force constant. Use this model to write an
having a piston the container was open to the atmosphere?
expression for the work that must be done to extend a DNA molecule by a
2A.3 Calculate the work done during the isothermal reversible expansion of distance x. Draw a graph of your conclusion.
a gas that satisfies the virial equation of state, eqn 1C.3. Evaluate (a) the work
104 2 The First Law
2A.6 A better model of a DNA molecule is the ‘one-dimensional freely jointed
chain’, in which a rigid unit of length l can only make an angle of 0° or 180 °
with an adjacent unit. In this case, the restoring force of a chain extended by
x = nl is given by
kT  1 +   n 2A.7 As a continuation of Problem 2A.6, (a) show that for small extensions of
F= ln =
2l  1 −   N the chain, when í  1, the restoring force is given by
where k is Boltzmann’s constant. (a) What is the magnitude of the force that
must be applied to extend a DNA molecule with N = 200 by 90 nm? (b) Plot
the restoring force against ν, noting that ν can be either positive or negative.
How is the variation of the restoring force with end-to-end distance different
from that predicted by Hooke’s law? (c) Keep in mind that the difference in
TOPIC 2B Enthalpy
Discussion questions
2B.1 Explain the difference between the change in internal energy and the
change in enthalpy accompanying a process.
Exercises
2B.1(a) When 229 J of energy is supplied as heat to 3.0 mol Ar(g), the
temperature of the sample increases by 2.55 K. Calculate the molar heat
capacities at constant volume and constant pressure of the gas.
2B.1(b) When 178 J of energy is supplied as heat to 1.9 mol of gas molecules,
the temperature of the sample increases by 1.78 K. Calculate the molar heat
capacities at constant volume and constant pressure of the gas.
2B.2(a) The constant-pressure heat capacity of a sample of a perfect gas was
found to vary with temperature according to the expression Cp/(J K−1) =
20.17 + 0.3665(T/K). Calculate q, w, and ΔH when the temperature is raised
from 25 °C to 100 °C (i) at constant pressure, (ii) at constant volume.
Problems
2B.1 The following data show how the standard molar constant-pressure heat
capacity of sulfur dioxide varies with temperature. By how much does the
standard molar enthalpy of SO2(g) increase when the temperature is raised
from 298.15 K to 1500 K?
T/K 300 500 700 900 1100 1300 1500
C< −1 −1
p, m /(J K mol ) 39.909 46.490 50.829 53.407 54.993 56.033 56.759
2B.2 The following data show how the standard molar constant-pressure heat
capacity of ammonia depends on the temperature. Use mathematical software
to fit an expression of the form of eqn 2B.8 to the data and determine the
values of a, b, and c. Explore whether it would be better to express the data as
Cp,m = α + βT + γT 2, and determine the values of these coefficients.
end-to-end distance from an equilibrium value is x = nl and, consequently,
dx = ldn = Nldν, and write an expression for the work of extending a DNA
molecule. (d) Calculate the work of extending a DNA molecule from ν = 0
to ν = 1.0. Hint: You must integrate the expression for w. The task can be
accomplished easily with mathematical software.
kT nkT
F≈ =
l Nl
(b) Is the variation of the restoring force with extension of the chain given in
part (a) different from that predicted by Hooke’s law? Explain your answer.
2B.2 Why is the heat capacity at constant pressure of a substance normally
greater than its heat capacity at constant volume?
2B.2(b) The constant-pressure heat capacity of a sample of a perfect gas was
found to vary with temperature according to the expression Cp/(J K−1) =
20.17 + 0.4001(T/K). Calculate q, w, and ΔH when the temperature is raised
from 25 °C to 100 °C (i) at constant pressure, (ii) at constant volume.
2B.3(a) When 3.0 mol O2 is heated at a constant pressure of 3.25 atm, its
temperature increases from 260 K to 285 K. Given that the molar heat capacity
of O2 at constant pressure is 29.4 J K−1 mol−1, calculate q, ΔH, and ΔU.
2B.3(b) When 2.0 mol CO2 is heated at a constant pressure of 1.25 atm, its
temperature increases from 250 K to 277 K. Given that the molar heat capacity
of CO2 at constant pressure is 37.11 J K−1 mol−1, calculate q, ΔH, and ΔU.
T/K 300 400 500 600 700 800 900 1000
C< −1 −1
p, m /(JK mol ) 35.678 38.674 41.994 45.229 48.269 51.112 53.769 56.244
2B.3 A sample consisting of 2.0 mol CO2 occupies a fixed volume of 15.0 dm3
at 300 K. When it is supplied with 2.35 kJ of energy as heat its temperature
increases to 341 K. Assume that CO2 is described by the van der Waals
equation of state (Topic 1C) and calculate w, ΔU, and ΔH.
2B.4 (a) Express (∂CV/∂V)T as a second derivative of U and find its relation to
(∂U/∂V)T and (∂Cp/∂p)T as a second derivative of H and find its relation to
(∂H/∂p)T. (b) From these relations show that (∂CV/∂V)T = 0 and (∂Cp/∂p)T = 0
for a perfect gas.

TOPIC 2C Thermochemistry
Discussion questions
2C.1 Describe two calorimetric methods for the determination of enthalpy
changes that accompany chemical processes.
Exercises
2C.1(a) For tetrachloromethane, ΔvapH< = 30.0 kJ mol−1. Calculate q, w, ΔH,
and ΔU when 0.75 mol CCl4(l) is vaporized at 250 K and 750 Torr.
2C.1(b) For ethanol, ΔvapH< = 43.5 kJ mol−1. Calculate q, w, ΔH, and ΔU when
1.75 mol C2H5OH(l) is vaporized at 260 K and 765 Torr.
2C.2(a) The standard enthalpy of formation of ethylbenzene is –12.5 kJ mol−1.
Calculate its standard enthalpy of combustion.
2C.2(b) The standard enthalpy of formation of phenol is –165.0 kJ mol−1.
Calculate its standard enthalpy of combustion.
2C.3(a) The standard enthalpy of combustion of cyclopropane is –2091 kJ
mol−1 at 25 °C. From this information and enthalpy of formation data for
CO2(g) and H2O(g), calculate the enthalpy of formation of cyclopropane. The
enthalpy of formation of propene is +20.42 kJ mol−1. Calculate the enthalpy of
isomerization of cyclopropane to propene.
2C.3(b) From the following data, determine ΔfH< for diborane, B2H6(g), at
298 K:
(1) B2 H6(g ) + 3 O2 (g ) → B2O3 (s) + 3 H2O(g) ∆ r H < = −1941 kJ mol −1
(2) 2 B(s) + 23 O2 (g ) → B2O3 (s) ∆ r H < = −2368 kJ mol −1
(3) H2(g ) + 12 O2 (g ) → H2O(g) ∆ r H < = −241.8 kJ mol −1
2C.4(a) Given that the standard enthalpy of formation of HCl(aq) is
−167 kJ mol−1, what is the value of ΔfH<(Cl−, aq)?
2C.4(b) Given that the standard enthalpy of formation of HI(aq) is
−55 kJ mol−1, what is the value of ΔfH<(I−, aq)?
2C.5(a) When 120 mg of naphthalene, C10H8(s), was burned in a bomb
calorimeter the temperature rose by 3.05 K. Calculate the calorimeter
constant. By how much will the temperature rise when 150 mg of phenol,
C6H5OH(s), is burned in the calorimeter under the same conditions?
2C.5(b) When 225 mg of anthracene, C14H10(s), was burned in a bomb
calorimeter the temperature rose by 1.75 K. Calculate the calorimeter
constant. By how much will the temperature rise when 125 mg of phenol,
C6H5OH(s), is burned in the calorimeter under the same conditions?
(ΔcH<(C14H10,s) = –7061 kJ mol−1.)
2C.6(a) Given the reactions (1) and (2) below, determine (i) ΔrH<and ΔrU< for
reaction (3), (ii) ΔfH< for both HCl(g) and H2O(g) all at 298 K.
(1) H2 (g ) + Cl 2 (g ) → 2 HCl(g) ∆ r H < = −184.62 kJ mol −1
(2) H2 (g ) + O2 (g ) → 2 H2O(g) ∆ r H < = −483.64 kJ mol −1
(3) 4 HCl(g) + O2 (g ) → 2 Cl 2 (g ) + 2 H2O(g)
Problems
2C.1 A sample of the sugar d-ribose (C5H10O5) of mass 0.727 g was placed
in a constant-volume bomb calorimeter and then ignited in the presence of
excess oxygen. The temperature rose by 0.910 K. In a separate experiment in
the same calorimeter, the combustion of 0.825 g of benzoic acid, for which the
internal energy of combustion is –3251 kJ mol−1, gave a temperature rise of
1.940 K. Calculate the enthalpy of formation of d-ribose.
Exercises and problems 105
2C.2 Distinguish between ‘standard state’ and ‘reference state’, and indicate
their applications.
2C.6(b) Given the reactions (1) and (2) below, determine (i) ΔrH< and ΔrU<
for reaction (3), (ii) ΔfH< for both HI(g) and H2O(g) all at 298 K.
(1) H2(g ) + I2(s) → 2 HI(g) ∆ r H < = +52.96 kJ mol −1
(2) 2 H2(g ) + O2(g) → 2 H2O(g) ∆ r H < = −483.64 kJ mol −1
(3) 4 HI(g) + O2(g ) → 2 I2 (s) + 2 H2O(g)
2C.7(a) For the reaction C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(g), ΔrU< =
–1373 kJ mol−1 at 298 K. Calculate ΔrH<.
2C.7(b) For the reaction 2 C6H5COOH(s) + 15 O2(g) → 14 CO2(g) + 6 H2O(g),
ΔrU< = –772.7 kJ mol−1 at 298 K. Calculate ΔrH<.
2C.8(a) From the data in Tables 2C.2 and 2C.3, calculate ΔrH< and ΔrU< at
(i) 298 K, (ii) 478 K for the reaction C(graphite) + H2O(g) → CO(g) + H2(g).
Assume all heat capacities to be constant over the temperature range of
interest.
2C.8(b) Calculate ΔrH< and ΔrU< at 298 K and ΔrH< at 427 K for the
hydrogenation of ethyne (acetylene) to ethene (ethylene) from the enthalpy of
combustion and heat capacity data in Tables 2C.5 and 2C.6. Assume the heat
capacities to be constant over the temperature range involved.
2C.9(a) Estimate ΔrH< (500 K) for the combustion of methane, CH4(g) +
2 O2(g) → CO2(g) + 2 H2O(g) by using the data on the temperature
dependence of heat capacities in Table 2B.1.
2C.9(b) Estimate ΔrH< (478 K) for the combustion of naphthalene,
C10H8(l) + 12 O2(g) → 10 CO2(g) + 4 H2O(g) by using the data on the
temperature dependence of heat capacities in Table 2B.1.
2C.10(a) Set up a thermodynamic cycle for determining the enthalpy of
hydration of Mg2+ ions using the following data: enthalpy of sublimation
of Mg(s), +167.2 kJ mol−1; first and second ionization enthalpies of Mg(g),
7.646 eV and 15.035 eV; dissociation enthalpy of Cl2(g), +241.6 kJ mol−1;
electron gain enthalpy of Cl(g), –3.78 eV; enthalpy of solution of MgCl2(s),
–150.5 kJ mol−1; enthalpy of hydration of Cl−(g), –383.7 kJ mol−1.
2C.10(b) Set up a thermodynamic cycle for determining the enthalpy of
hydration of Ca2+ ions using the following data: enthalpy of sublimation
of Ca(s), +178.2 kJ mol−1; first and second ionization enthalpies of Ca(g),
589.7 kJ mol−1 and 1145 kJ mol−1; enthalpy of vaporization of bromine,
+30.91 kJ mol−1; dissociation enthalpy of Br2(g), +192.9 kJ mol−1; electron
gain enthalpy of Br(g), –331.0 kJ mol−1; enthalpy of solution of CaBr2(s),
–103.1 kJ mol−1; enthalpy of hydration of Br−(g), -289 kJ mol−1.
2C.2 The standard enthalpy of formation of bis(benzene)chromium
was measured in a calorimeter. It was found for the reaction
Cr(C6H6)2(s) → Cr(s) + 2 C6H6(g) that ΔrU<(583 K) = +8.0 kJ mol−1. Find
the corresponding reaction enthalpy and estimate the standard enthalpy
of formation of the compound at 583 K. The constant-pressure molar
heat capacity of benzene is 136.1 J K−1 mol−1 in its liquid range and
81.67 J K−1 mol−1 as a gas.
106 2 The First Law

2C.3‡ From the enthalpy of combustion data in Table 2C.1 for the alkanes
methane through octane, test the extent to which the relation ΔcH< =
k{(M/(g mol−1)}n holds and find the numerical values for k and n.
Predict ΔcH< for decane and compare to the known value.
2C.4‡ Kolesov et al. reported the standard enthalpy of combustion and of
formation of crystalline C60 based on calorimetric measurements (V.P.
2C.8 Figure 2.1 shows the experimental DSC scan of hen white lysozyme
(G. Privalov et al., Anal. Biochem. 79, 232 (1995)) converted to joules
(from calories). Determine the enthalpy of unfolding of this protein by
integration of the curve and the change in heat capacity accompanying the
transition.

Excess heat capacity, Cp,ex/(mJ °C–1)

Kolesov et al., J. Chem. Thermodynamics 28, 1121 (1996)). In one of their 9
runs, they found the standard specific internal energy of combustion to be
–36.0334 kJ g−1 at 298.15 K. Compute ΔcH< and ΔfH< of C60.
2C.5‡ A thermodynamic study of DyCl3 (E.H.P. Cordfunke et al., J. Chem.
6
Thermodynamics 28, 1387 (1996)) determined its standard enthalpy of
formation from the following information

(1) DyCl3 (s) → DyCl3 (aq, in 4.0 M HCl) ∆ r H < = −180.06 kJ mol −1 3
(2) Dy(s) + 3 HCl(aq, 4.0 M) → DyCl3 (aq, in 4.0 M HCl(aq)) + 23 H2 (g )
∆ r H < = −699.43 kJ mol −1
(3) 1 H (g ) + 1 Cl (g ) → HCl(aq , 4.0 M)
2 2 2 2 ∆ r H < = −158.31 kJ mol −1 0
30 45 60 75 90
Determine ΔfH<(DyCl3, s) from these data. Temperature, θ/°C

2C.6‡ Silylene (SiH2) is a key intermediate in the thermal decomposition Figure 2.1 The experimental DSC scan of hen white lysozyme.
of silicon hydrides such as silane (SiH4) and disilane (Si2H6). H.K. Moffat
et al. (J. Phys. Chem. 95, 145 (1991)) report ΔfH<(SiH2) = +274 kJ mol−1. If
2C.9 An average human produces about 10 MJ of heat each day through
ΔfH<(SiH4) = +34.3 kJ mol−1 and ΔfH<(Si2H6) = +80.3 kJ mol−1, compute the
metabolic activity. If a human body were an isolated system of mass 65 kg with
standard enthalpies of the following reactions:
the heat capacity of water, what temperature rise would the body experience?
(a) SiH4(g) → SiH2(g) + H2(g) Human bodies are actually open systems, and the main mechanism of heat
(b) Si2H6(g) → SiH2(g) + SiH4(g) loss is through the evaporation of water. What mass of water should be
evaporated each day to maintain constant temperature?
2C.7 As remarked in Problem 2B.2, it is sometimes appropriate to express
the temperature dependence of the heat capacity by the empirical expression 2C.10 In biological cells that have a plentiful supply of oxygen, glucose is
Cp,m = α + βT + γ T 2. Use this expression to estimate the standard enthalpy of oxidized completely to CO2 and H2O by a process called aerobic oxidation.
combustion of methane at 350 K. Use the following data: Muscle cells may be deprived of O2 during vigorous exercise and, in that
case, one molecule of glucose is converted to two molecules of lactic acid
(CH3CH(OH)COOH) by a process called anaerobic glycolysis. (a) When
α/(J K−1 mol−1) β/(mJ K−2 mol−1) γ /(μJ K−3 mol−1) 0.3212 g of glucose was burned in a bomb calorimeter of calorimeter
constant 641 J K−1 the temperature rose by 7.793 K. Calculate (i) the
CH4(g) 14.16 75.5 –17.99
standard molar enthalpy of combustion, (ii) the standard internal energy of
CO2(g) 26.86 6.97 –0.82 combustion, and (iii) the standard enthalpy of formation of glucose.
O2(g) 25.72 12.98 –3.862 (b) What is the biological advantage (in kilojoules per mole of energy
released as heat) of complete aerobic oxidation compared with anaerobic
H2O(g) 30.36 9.61 1.184 glycolysis to lactic acid?

TOPIC 2D State functions and exact differentials

Discussion questions
2D.1 Suggest (with explanation) how the internal energy of a van der Waals 2D.2 Explain why a perfect gas does not have an inversion temperature.
gas should vary with volume at constant temperature.

Exercises
2D.1(a) Estimate the internal pressure, πT , of water vapour at 1.00 bar and 2D.2(a) For a van der Waals gas, π T = a /Vm
2 . Calculate ΔU for the isothermal
m
400 K, treating it as a van der Waals gas. Hint: Simplify the approach by expansion of nitrogen gas from an initial volume of 1.00 dm3 to 20.00 dm3 at
estimating the molar volume by treating the gas as perfect. 298 K. What are the values of q and w?
2D.1(b) Estimate the internal pressure, πT , of sulfur dioxide at 1.00 bar and 2D.2(b) Repeat Exercise 2D.2(a) for argon, from an initial volume of 1.00 dm3
298 K, treating it as a van der Waals gas. Hint: Simplify the approach by to 30.00 dm3 at 298 K.
estimating the molar volume by treating the gas as perfect.

‡ These problems were provided by Charles Trapp and Carmen Giunta.

 Exercises and problems 107

2D.3(a) The volume of a certain liquid varies with temperature as 2D.5(a) Given that μ = 0.25 K atm−1 for nitrogen, calculate the value of its
isothermal Joule–Thomson coefficient. Calculate the energy that must be
V = V < {0.75 + 3.9 × 10−4 (T/K) + 1.48 × 10−6 (T/K )2 } supplied as heat to maintain constant temperature when 10.0 mol N2 flows
through a throttle in an isothermal Joule–Thomson experiment and the
where V< is its volume at 300 K. Calculate its expansion coefficient, α, at 320 K. pressure drop is 85 atm.
2D.3(b) The volume of a certain liquid varies with temperature as 2D.5(b) Given that μ = 1.11 K atm−1 for carbon dioxide, calculate the value of
its isothermal Joule–Thomson coefficient. Calculate the energy that must be
V = V < {0.77 + 3.7 × 10−4 (T/K) + 1.52 × 10−6 (T/K )2 } supplied as heat to maintain constant temperature when 10.0 mol CO2 flows
through a throttle in an isothermal Joule–Thomson experiment and the
where V< is its volume at 298 K. Calculate its expansion coefficient, α, at 310 K.
pressure drop is 75 atm.
2D.4(a) The isothermal compressibility of water at 293 K is 4.96 × 10−5 atm−1.
Calculate the pressure that must be applied in order to increase its density by
0.10 per cent.
2D.4(b) The isothermal compressibility of lead at 293 K is 2.21 × 10−6 atm−1.
Calculate the pressure that must be applied in order to increase its density by
0.10 per cent.

Problems
2D.1‡ In 2006, the Intergovernmental Panel on Climate Change (IPCC) 2D.9 Use the fact that (∂U /∂V )T = a /Vm
2 for a van der Waals gas (Topic 1C)

considered a global average temperature rise of 1.0–3.5 °C likely by the year to show that μCp,m ≈ (2a/RT) – b by using the definition of μ and appropriate
2100, with 2.0 °C its best estimate. Predict the average rise in sea level due to relations between partial derivatives. Hint: Use the approximation pVm ≈ RT
thermal expansion of sea water based on temperature rises of 1.0 °C, 2.0 °C, when it is justifiable to do so.
and 3.5 °C given that the volume of the Earth’s oceans is 1.37 × 109 km3 and
2D.10‡ Concerns over the harmful effects of chlorofluorocarbons on
their surface area is 361 × 106 km2, and state the approximations which go into
stratospheric ozone have motivated a search for new refrigerants. One such
the estimates.
alternative is 2,2-dichloro-1,1,1-trifluoroethane (refrigerant 123). Younglove
2D.2 The heat capacity ratio of a gas determines the speed of sound in it and McLinden published a compendium of thermophysical properties of this
through the formula cs = (γ RT/M)1/2, where γ  = Cp/CV and M is the molar mass substance (B.A. Younglove and M. McLinden, J. Phys. Chem. Ref. Data 23,
of the gas. Deduce an expression for the speed of sound in a perfect gas of 7 (1994)), from which properties such as the Joule–Thomson coefficient μ
(a) diatomic, (b) linear triatomic, (c) nonlinear triatomic molecules at high can be computed. (a) Compute μ at 1.00 bar and 50 °C given that (∂H/∂p)T =
temperatures (with translation and rotation active). Estimate the speed of –3.29 × 103 J MPa−1 mol−1 and Cp,m = 110.0 J K−1 mol−1. (b) Compute the
sound in air at 25 °C. temperature change which would accompany adiabatic expansion of 2.0 mol
of this refrigerant from 1.5 bar to 0.5 bar at 50 °C.
2D.3 Starting from the expression Cp – CV = T(∂p/∂T)V(∂V/∂T)p, use the
appropriate relations between partial derivatives to show that 2D.11‡ Another alternative refrigerant (see preceding problem) is
1,1,1,2-tetrafluoroethane (refrigerant HFC-134a). A compendium of
T (∂V / ∂T )2p thermophysical properties of this substance has been published (R. Tillner-
C p − CV = Roth and H.D. Baehr, J. Phys. Chem. Ref. Data 23, 657 (1994)) from which
(∂V / ∂p)T
properties such as the Joule–Thomson coefficient μ can be computed. (a)
Evaluate Cp – CV for a perfect gas. Compute μ at 0.100 MPa and 300 K from the following data (all referring to
300 K):
2D.4 (a) Write expressions for dV and dp given that V is a function of p and T
p/MPa 0.080 0.100 0.12
and p is a function of V and T. (b) Deduce expressions for d ln V and d ln p in
terms of the expansion coefficient and the isothermal compressibility. Specific enthalpy/(kJ kg−1) 426.48 426.12 425.76
2D.5 Rearrange the van der Waals equation of state, p = nRT/(V – nb) – (The specific constant-pressure heat capacity is 0.7649 kJ K−1 kg−1.) (b)
n2a/V 2, to give an expression for T as a function of p and V (with n constant). Compute μ at 1.00 MPa and 350 K from the following data (all referring to
Calculate (∂T/∂p)V and confirm that (∂T/∂p)V = 1/(∂p/∂T)V . Go on to confirm 350 K):
Euler’s chain relation (Mathematical background 2).
p/MPa 0.80 1.00 1.2
2D.6 Calculate the isothermal compressibility and the expansion coefficient
Specific enthalpy/(kJ kg−1) 461.93 459.12 42B.15
of a van der Waals gas (see Problem 2D.5). Show, using Euler’s chain relation
(Mathematical background 2), that κTR = α(Vm – b). (The specific constant-pressure heat capacity is 1.0392 kJ K−1 kg−1.)
2D.7 The speed of sound, cs, in a gas of molar mass M is related to the ratio of
heat capacities γ by cs = (γ RT/M)1/2. Show that cs = (γ p/ρ)1/2, where ρ is the
mass density of the gas. Calculate the speed of sound in argon at 25 °C.
2D.8‡ A gas obeying the equation of state p(V – nb) = nRT is subjected to a
Joule–Thomson expansion. Will the temperature increase, decrease, or remain
the same?
108 2 The First Law
TOPIC 2E Adiabatic changes
Discussion questions
2E.1 Why are adiabats steeper than isotherms?
Exercises
2E.1(a) Use the equipartition principle to estimate the values of γ  = Cp/CV
for gaseous ammonia and methane. Do this calculation with and without
the vibrational contribution to the energy. Which is closer to the expected
experimental value at 25 °C?
2E.1(b) Use the equipartition principle to estimate the value of γ  = Cp/CV
for carbon dioxide. Do this calculation with and without the vibrational
contribution to the energy. Which is closer to the expected experimental
value at 25 °C?
2E.2(a) Calculate the final temperature of a sample of argon of mass 12.0 g that
is expanded reversibly and adiabatically from 1.0 dm3 at 273.15 K to 3.0 dm3.
2E.2(b) Calculate the final temperature of a sample of carbon dioxide of mass
16.0 g that is expanded reversibly and adiabatically from 500 cm3 at 298.15 K
to 2.00 dm3.
2E.3(a) A sample consisting of 1.0 mol of perfect gas molecules with
CV = 20.8 J K−1 is initially at 4.25 atm and 300 K. It undergoes reversible
adiabatic expansion until its pressure reaches 2.50 atm. Calculate the final
volume and temperature and the work done.
Problem
2E.1 The constant-volume heat capacity of a gas can be measured by observing
the decrease in temperature when it expands adiabatically and reversibly. The
value of γ  = Cp/CV can be inferred if the decrease in pressure is also measured
and the constant-pressure heat capacity deduced by combining the two values.
Integrated activities
2.1 Give examples of state functions and discuss why they play a critical role in
thermodynamics.
2.2 The thermochemical properties of hydrocarbons are commonly investigated
by using molecular modelling methods. (a) Use software to predict ΔcH< values
for the alkanes methane through pentane. To calculate ΔcH< values, estimate
the standard enthalpy of formation of CnH2n+2(g) by performing semi-empirical
calculations (for example, AM1 or PM3 methods) and use experimental
standard enthalpy of formation values for CO2(g) and H2O(l). (b) Compare
your estimated values with the experimental values of ΔcH< (Table 2C.4)
and comment on the reliability of the molecular modelling method. (c) Test
the extent to which the relation ΔcH< = constant × {(M/(g mol−1)}n holds and
determine the numerical values of the constant and n.
2E.2 Why do heat capacities play a role in the expressions for adiabatic
expansion?
2E.3(b) A sample consisting of 2.5 mol of perfect gas molecules with
Cp,m = 20.8 J K−1 mol−1 is initially at 240 kPa and 325 K. It undergoes reversible
adiabatic expansion until its pressure reaches 150 kPa. Calculate the final
volume and temperature and the work done.
2E.4(a) A sample of carbon dioxide of mass 2.45 g at 27.0 °C is allowed to
expand reversibly and adiabatically from 500 cm3 to 3.00 dm3. What is the
work done by the gas?
2E.4(b) A sample of nitrogen of mass 3.12 g at 23.0 °C is allowed to expand
reversibly and adiabatically from 400 cm3 to 2.00 dm3. What is the work done
by the gas?
2E.5(a) Calculate the final pressure of a sample of carbon dioxide that expands
reversibly and adiabatically from 67.4 kPa and 0.50 dm3 to a final volume of
2.00 dm3. Take γ  = 1.4.
2E.5(b) Calculate the final pressure of a sample of water vapour that expands
reversibly and adiabatically from 97.3 Torr and 400 cm3 to a final volume of
5.0 dm3. Take γ  = 1.3.
A fluorocarbon gas was allowed to expand reversibly and adiabatically to
twice its volume; as a result, the temperature fell from 298.15 K to 248.44 K
and its pressure fell from 202.94 kPa to 81.840 kPa. Evaluate Cp.
2.3 Use mathematical software, a spreadsheet, or the Living graphs on the web
site for this book to:
(a) Calculate the work of isothermal reversible expansion of 1.0 mol CO2(g)
at 298 K from 1.0 m3 to 3.0 m3 on the basis that it obeys the van der Waals
equation of state.
(b) Explore how the parameter γ affects the dependence of the pressure on the
volume. Does the pressure–volume dependence become stronger or weaker
with increasing volume?
 Multivariate calculus 109

Mathematical background 2 Multivariate calculus

A thermodynamic property of a system typically depends on
Brief illustration MB2.1 Partial derivatives
a number of variables, such as the internal energy depending
on the amount, volume, and temperature. To understand how Suppose that f(x,y) = ax 3y + by 2 (the function plotted in Fig.
these properties vary with the conditions we need to under- MB2.1) then
stand how to manipulate their derivatives. This is the field of
multivariate calculus, the calculus of several variables.  ∂f   ∂f 
 ∂x  = 3ax y  ∂y  = ax + 2by
2 3

y x

MB2.1 Partial derivatives Then, when x and y undergo infinitesimal changes, f changes
A partial derivative of a function of more than one variable, by
such as f(x,y), is the slope of the function with respect to one of df = 3ax 2 y dx + (ax 3 + 2by )dy
the variables, all the other variables being held constant (Fig.
MB2.1). Although a partial derivative shows how a function To verify that the order of taking the second partial derivative
changes when one variable changes, it may be used to deter- is irrelevant, we form
mine how the function changes when more than one variable
 ∂  ∂f    ∂(3ax 2 y ) 
changes by an infinitesimal amount. Thus, if f is a function of  ∂y  ∂x   =  ∂y  = 3ax
2

x and y, then when x and y change by dx and dy, respectively, f  y  x

x
changes by  ∂  ∂f    ∂(ax 3 + 2by ) 
 ∂x  ∂y   =   = 3ax
2

x y
∂x
y
 ∂f   ∂f 
d f =   dx +   dy (MB2.1)
 ∂x  y  ∂y  x
In the following, z is a variable on which x and y depend (for
where the symbol ∂ (‘curly d’) is used (instead of d) to denote example, x, y, and z might correspond to p, V, and T).
a partial derivative and the subscript on the parentheses indi- Relation 1. When x is changed at constant z:
cates which variable is being held constant. The quantity df is
also called the differential of f. Successive partial derivatives  ∂f   ∂f   ∂f   ∂y 
may be taken in any order:  ∂x  =  ∂x  +  ∂y   ∂x  (MB2.3a)
z y x z

 ∂  ∂f    ∂  ∂ f   Relation 2
 ∂y  ∂x   =  ∂x  ∂y   (MB2.2)
 y  xy
x  ∂y  1
 ∂x  = (∂x / ∂y ) (MB2.3b)
z z

Relation 3
(∂f/∂x)y
(∂f/∂y)x
 ∂x   ∂x   ∂z 
 ∂y  = −  ∂z   ∂y  (MB2.3c)
z y x
f(x,y)
By combining Relations 2 and 3 we obtain the Euler chain
relation:

x  ∂y   ∂x   ∂z 
 ∂x   ∂z   ∂y  = −1 Euler chain relation (MB2.4)
z y x

y
MB2.2 Exact differentials
Figure MB2.1 A function of two variables, f(x,y), as depicted
by the coloured surface and the two partial derivatives, The relation in eqn MB2.2 is the basis of a test for an exact dif-
(∂f/∂x)y and (∂f/∂y)x, the slope of the function parallel to ferential; that is, the test of whether
the x- and y-axes, respectively. The function plotted here is
f(x,y) = ax3y + by2 with a = 1 and b = –2. df = g (x , y )dx + h(x , y )dy (MB2.5)
110 Mathematical background 2

has the form in eqn MB2.1. If it has that form, then g can be
identified with (∂f/∂x)y and h can be identified with (∂f/∂y)x.  ∂f   ∂(ax 3 y + k)  dk
 ∂y  =   = ax + dy = ax + 2by
3 3

Then eqn MB2.2 becomes x

∂ y
x

 ∂g   ∂h  Therefore
 ∂y  =  ∂x  Test for exact differential (MB2.6)
dk
x y
= 2by
dy

Brief illustration MB2.2 Exact differentials from which it follows that k = by2 + constant. We have found,
therefore, that
Suppose, instead of the form df = 3ax 2ydx + (ax 3 + 2by)dy in
the previous Brief illustration, we were presented with the f (x , y )= ax 3 y + by 2 + constant
expression
which, apart from the constant, is the original function in the
g( x , y ) h( x , y )
   Brief illustration MB2.1. The value of the constant is pinned
df = 3ax 2 y dx + (ax 2 + 2by )dy down by stating the boundary conditions; thus, if it is known
that f(0,0) = 0, then the constant is zero.
with ax 2 in place of ax 3 inside the second parentheses. To test
whether this is an exact differential, we form
To demonstrate that the integral of df is independent of the
 ∂g   ∂(3ax 2 y ) 
 ∂y  =  ∂y  = 3ax path is now straight forward. Because df is a differential, its
2

x x
integral between the limits a and b is
 ∂h   ∂(ax 2 + 2by ) 
 ∂x  =  ∂x  = 2ax b

y y
These two expressions are not equal, so this form of df is not an
exact differential and there is not a corresponding integrated
function of the form f(x,y).
If df is exact, then we can do two things:
∫ df = f (b)− f (a)
a
The value of the integral depends only on the values at the end
points and is independent of the path between them. If df is
not an exact differential, the function f does not exist, and this
argument no longer holds. In such cases, the integral of df does
depend on the path.

• From a knowledge of the functions g and h we can

Brief illustration MB2.4 Path-dependent integration
reconstruct the function f.
• Be confident that the integral of df between specified Consider the inexact differential (the expression with ax 2 in
limits is independent of the path between those limits. place of ax3 inside the second parentheses):

The first conclusion is best demonstrated with a specific df = 3ax 2 y dx + (ax 2 + 2by )dy
example.
Suppose we integrate df from (0,0) to (2,2) along the two paths
shown in Fig. MB2.2. Along Path 1,

Brief illustration MB2.3 The reconstruction (0,2) y=2 (2,2)

of an equation
x=0

x=2

We consider the differential df = 3ax 2ydx + (ax3 + 2by)dy, which

we know to be exact. Because (∂f/∂x)y = 3ax 2y, we can integrate y
with respect to x with y held constant, to obtain Path 2 Path 1

∫ ∫ ∫
f = df = 3ax 2 y dx = 3ay x 2 dx = ax 3 y + k y=0 (2,0)
x
where the ‘constant’ of integration k may depend on y (which
has been treated as a constant in the integration), but not on Figure MB2.2 The two integration paths referred to in Brief
x. To find k(y), we note that (∂f/∂y)x = ax3 + 2by, and therefore illustration MB2.4.
 Multivariate calculus 111

2 ,0 2 ,2 g( x , y ) h( x , y )

∫ ∫ ∫
df = 3ax 2 y dx + (ax 2 + 2by )dy   
 
Path 1 0 ,0 2 ,0 df ′ = 3ax y dx + ax m+2 y n dy
m+2 n+1

2 2
= 0 + 4a ∫ dy + 2b∫
0 0
y dy = 8a + 4b We evaluate the following two partial derivatives:

whereas along Path 2,  ∂g   ∂(3ax m+2 y n+1) 

 ∂y  =   = 3a(n + 1)x y
m +2 n

x
∂y
2 ,2 0 ,2 x

∫Path 2
df = ∫ 0 ,2
3ax 2 y dx + ∫0 ,0
(ax 2 + 2by )dy  ∂h   ∂(ax m+2 y n ) 
 ∂x  =  ∂x  = a(m + 2)x y
m+1 n

2 2 y y
= 6a ∫ 0
x 2 dx + 0 + 2b ∫ 0
y dy = 16a + 4b
For the new differential to be exact, these two partial deriva-
The two integrals are not the same. tives must be equal, so we write

3a(n + 1)x m +2 y n = a(m + 2)x m +1 y n

An inexact differential may sometimes be converted into an which simplifies to

exact differential by multiplication by a factor known as an inte-
grating factor. A physical example is the integrating factor 1/T 3(n + 1)x = m + 2
that converts the inexact differential dqrev into the exact differ-
The only solution that is independent of x is n = –1 and m = –2.
ential dS in thermodynamics (Topic 3A).
It follows that

df ′ = 3adx +(a/y )dy

Brief illustration MB2.5 An integrating factor
is an exact differential. By the procedure already illustrated, its
We have seen that the differential df = 3ax 2ydx + (ax 2 + 2by) integrated form is f ′(x,y) = 3ax + a ln y + constant.
dy is inexact; the same is true when we set b = 0 and consider
df = 3ax 2ydx + ax 2dy instead. Suppose we multiply this df by
xmyn and write xmyndf = df ′, then we obtain